Compositions and Methods of Using Polyamidopolyamines and Non-Polymeric Amidoamines

ABSTRACT

Compositions comprising a polyamidopolyamine and/or a non-poly-meric amidoamine are disclosed for imparting multiple desired characteristics to a variety of industrial compositions. In certain embodiments, these compositions are prepared by condensing a C 4  to C 16  poly basic acid, monobasic acid or derivative thereof with a polyamine comprising a primary amino group, and in the presence of an optional organic diluent. Certain specific polyamidopolyamine and a non-polymeric amidoamine formulae and compositions containing same are disclosed, as are methods of use of these compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of the priority of US Provisional Patent Application No. 62/147,840, filed Apr. 15, 2015, which application is incorporated herein by reference.

BACKGROUND OF THE INVENTION

Various compositions for industrial use require specific characteristics for use, e.g., paint requires a certain amount of rheology control and coating ability, as well as a specified amount of bioresistance. Analogously metal working fluids require lubricity, load carrying ability, the control of foaming during use and microorganism growth control. Still other compositions abound that have specific and varied requires for anti-foaming or defoaming during use, and also bioresistance, etc. Generally to provide a composition with multiple specific characteristics for successful use a number of additives must be combined in proportions appropriate to provide the characteristics. The development of such compositions is thus expensive and time-consuming, with the developer attempting to identify and combine cooperative components in the correct amounts and concentrations to achieve a useful composition that has characteristics is as close to a specified list as possible.

Formulation of such compositions, requiring multiple different components to achieve different end goals when in combination is both challenging and costly. There is a need in all of the industrial arts for compositions which may be readily prepared using a minimal number of components to lessen the environmental impact, and yet retaining or having desired multiple characteristics of lubricity, low foaming, bioresistance, etc.

SUMMARY OF THE INVENTION

In one aspect, a composition is provided that comprises a polyamidopolyamine, which is a linear, cyclic, branched or cross-linked amide comprising a primary amine group. In still other embodiments, the polyamidopolyamines comprises one or more primary amine groups. In one embodiment, the polyamidopolyamine has a molecular weight of about 500 to about 100,000. In one aspect, the polyamidopolyamine is produced by the reaction of a polybasic acid and primary polyamine containing at least three primary amino groups in the optional presence of a hydroxyl-containing organic diluent. In another aspect, the polyamidopolyamine is produced by sequential condensation reactions of a polybasic acid and polyamine in the optional presence of a hydroxyl-containing organic diluent. In still another aspect, the polyamidopolyamine is produced by the reaction of a polybasic acid, a monobasic acid, and primary polyamine. These polyamidopolyamines or compositions containing them surprisingly provide to a resulting composition multiple properties selected from antimicrobial properties, bioresistant properties, defoaming properties, anti-foaming properties, lubricating and load-carrying properties and any combinations of two or more of those properties.

In another aspect, a method for preparing a composition comprising a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group is provided. The method comprises condensing (i) a polyamine comprising a primary amino group (e.g., one or more) and (ii) a C₃ to C₁₆ polybasic acid or derivative thereof, optionally in the presence of an organic hydroxyl-containing diluent as solvent. In one embodiment, the condensation reaction occurs in the presence of excess polyamine when the polyamine is also used as solvent.

In still another aspect, a method for providing such compositions containing polyamidopolyamines of molecular weights greater than about 100,000 comprises repetitive steps. A first step includes reacting a polybasic acid with a polyamine and an optional hydroxyl-containing solvent to produce a first polyamidopolyamine as a reaction product; reacting the reaction product with the same or different a polybasic acid and an optional hydroxyl-containing solvent to produce another polyamidopolyamine as a subsequent reaction product. Additional sequential condensation reactions are performed by reacting the polyamidopolyamine reaction product of each preceding condensation reaction with the same or different polybasic acid and an optional hydroxyl-containing solvent. The reaction sequence may be terminated by addition of a monobasic acid when the composition demonstrates a desired characteristic selected from anti-foaming, defoaming, lubricity, load-carrying, bioresistance, antimicrobial activity or any combination thereof.

In one aspect, a composition is provided that comprises a non-polymeric amidoamine, which is a linear or branched amide comprising a primary amine group. In still other embodiments, the non-polymeric amidoamine comprises two or more primary amine groups. In one embodiment, the non-polymeric amidoamine has a molecular weight of about 290 to about 5000.

In another aspect, the composition that comprises a non-polymeric amidoamine also comprises a non-polymeric amide, which is a linear or branched amide comprising no primary amine group. In one embodiment, the non-polymeric amide has a molecular weight of about 290 to about 5000.

In another aspect, the compositions comprising the non-polymeric amidoamines described above are produced by the reaction of a monobasic acid and a primary amine comprising a primary amino group in the optional presence of a hydroxyl-containing organic diluent. These non-polymeric amidoamines or compositions containing them are characterized by one, or multiple, properties selected from antimicrobial properties, bioresistant properties, defoaming properties, anti-foaming properties and/or lubricating and load-carrying properties.

In still another aspect, compositions as described herein comprising a polyamidopolyamine and a non-polymeric amidoamine are produced by a condensation reaction comprising a polybasic acid, a monobasic acid with a primary amine or polyamine, or multiples of each component in the optional presence of a hydroxyl-containing organic diluent.

Still other aspects include various methods of using the composition and making them. These other aspects and advantages of the invention will be readily apparent from the following detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing bacterial count over time measured in colony forming units (cfu)/ml of deionized water containing a mixed bacterial culture treated with a composition comprising polyamidopolyamine (3533-171) described herein and in Example 1 below. FIG. 1 also indicates that the polyamidopolyamine-containing composition 3533-171 shows marked and quick bacterial growth inhibition rate, i.e., anti-microbial activity, at the concentration, i.e., 0.75% by weight in deionized water. All dilutions are in deionized water (DI).

FIG. 2 is a graph showing bacterial count over time measured in cfu/ml of deionized water containing a mixed bacterial culture treated with a polyamidopolyamine-containing composition 3587-17 described herein and in Example 2 below. FIG. 2 indicates that the polyamidopolyamine-containing composition 3587-17 shows marked and quick bacterial growth inhibition rate, i.e., anti-microbial activity, at the concentration, i.e., 0.75% by weight in deionized water. All dilutions are in deionized water (DI).

FIG. 3 is a graph showing bacterial count over time measured in cfu/ml of deionized water containing a mixed bacterial culture treated with a polyamidopolyamine-containing composition 3581-5 described herein and in Example 3 below. FIG. 3 indicates that the polyamidopolyamine-containing composition (3581-5) shows marked and quick bacterial growth inhibition rate, i.e., anti-microbial activity, at the concentration, i.e., 0.75% by weight in deionized water. All dilutions are in deionized water (DI).

FIG. 4 is a graph showing the comparative lubrication ability of the polyamidopolyamine-containing compositions 3533-171, 3587-17 and 3581-5 of Examples 1-3 vs. that of the HOCUT® 767 commercial synthetic metal removal fluid (Houghton International Inc.) as described in Example 4 below.

FIG. 5 is a cooling curve showing the comparison of polyamidopolyamine reaction products with water and Aqua Quench 260 (AQ260). AQ 260 is a commercial product supplied by Houghton International to slow down the quenching effect of water and its curve is shown as a broken line (i.e., large dashes). The curve for water is a solid line. The experimental polyamidopolyamine reaction product 3587-193 has a curve formed by small dashes. Product 3587-193 is a polyamidopolyamine, the reaction of Huntsman Jeffamine T403 (10 moles) with adipic acid (9 moles). The reaction is performed in approximately 44% dipropylene glycol (DPG). The DPG remains in the reaction mixture. Cloud point (1%) approximately 81° F. The cooling curve measurements were made using the IVF quenchometer.

FIG. 6 shows the curves produced by the method described in FIG. 5 using product 3533-85-2 in the IVF method. 3533-85-2 is the product of a condensation reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1 mole). Cloud point (0.75%), approximately 86° F.; weight average molecular weight, 2,240; determined by GPC. The curves are water (solid line), 260-1 (a broken line) and 3533-85-2 (line of small dashes).

FIG. 7 shows the curves produced by the method described in FIG. 5 using product 3587-17-2 in the IVF method. 3587-17-2 is the product of a condensation reaction of Huntsman Jeffamine T 403 (2 moles) with azelaic acid. The reaction is run in 45% triethanolamine. The DPG and TEA are also used as solvents for the reactions and also form the intermediate ester which is then converted to amide, releasing that solvent. The triethanolamine remains in the reaction mixture. Cloud point 0.75%, approximately 75° F. The curves are water (solid line), 260-1 (a broken line) and 3587-17-2 (line of small dashes).

FIG. 8 shows the curves produced by the method described in FIG. 5 using product 3587-203-2 in the IVF method. 3587-203-2 is a product of the condensation reaction of Huntsman Jeffamine T 403 (5 moles) with adipic acid (4 moles). Cloud point was cloudy at ambient, about 70° F., but becomes clear on cooling. The average molecular weight by GPC is 6,240 daltons. The curves are water (solid line), 260-1 (a broken line) and 3587-203-2 (line of small dashes).

FIG. 9 shows the curves produced by the method described in FIG. 5 using product 3533-171-1 in the IVF method. 3533-171-1 is the product of the condensation reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1 mole) with about 12% water added when the reaction is cooled below 90° C. The water acts as a solvent to reduce the viscosity of the neat product to make it more flowable. Cloud point, about 88° F. The curves are water (solid line), 260-1 (a broken line) and 3533-171-1 (line of small dashes).

DETAILED DESCRIPTION OF THE INVENTION

Described herein are compositions containing polyamidopolyamines and/or non-polymeric amidoamines, which compositions impart multiple desirable characteristics to the resulting industrial composition, including one or more of lubricity, bioresistance, anti-foaming, no-foaming, and/or antimicrobial properties.

Various components or characteristics of the compositions containing the polyamidopolyamines and/or non-polymeric amidoamines are described as follows.

The term “alkyl” is used herein to refer to both straight- and branched-chain saturated aliphatic hydrocarbon groups. In one embodiment, an alkyl group has 1 to about 30 carbon atoms (i.e., C₁, C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, or C₃₀). In a further embodiment, an alkyl group has 1 to about 10 carbon atoms (i.e., C₁, C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀). In another embodiment, an alkyl group has 4 to about 10 carbon atoms (i.e., C₄, C₅, C₆, C₇, C₈, C₉, or C₁₀). In a further embodiment, an alkyl group has 5 to about 10 carbon atoms (i.e., C₅, C₆, C₇, C₈, C₉, or C₁₀).

The term “cycloalkyl” is used herein to refer to cyclic, saturated aliphatic hydrocarbon groups. In one embodiment, a cycloalkyl group has 5 to about 10 carbon atoms (i.e., C₅, C₆, C₇, C₈, C₉, or C₁₀).

The term “alkenyl” is used herein to refer to both straight- and branched-chain alkyl groups having one or more carbon-carbon double bonds. In one embodiment, an alkenyl group has 2 to about 30 carbon atoms (i.e., C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, or C₃₀). In a further embodiment, an alkenyl group has 2 to about 10 carbon atoms (i.e., C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀). In another embodiment, an alkenyl group has 4 to about 10 carbon atoms (i.e., C₄, C₅, C₆, C₇, C₈, C₉, or C₁₀). In a further embodiment, an alkenyl group has 5 to about 10 carbon atoms (i.e., C₅, C₆, C₇, C₈, C₉, or C₁₀). In another embodiment, an alkenyl group has 1 or 2 carbon-carbon double bonds.

The term “alkynyl” is used herein to refer to both straight- and branched-chain alkyl groups having one or more carbon-carbon triple bonds. In one embodiment, an alkynyl group has 2 to about 30 carbon atoms (i.e., C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, or C₃₀). In a further embodiment, an alkynyl group has 2 to about 10 carbon atoms (i.e., C₂, C₃, C₄, C₅ C₆, C₇, C₈, C₉, or C₁₀). In another embodiment, an alkynyl group has 4 to about 10 carbon atoms (i.e., C₄, C₅, C₆, C₇, C₈, C₉, or C₁₀). In a further embodiment, an alkynyl group has 5 to about 10 carbon atoms (i.e., C₅, C₆, C₇, C₈, C₉, or C₁₀). In another embodiment, an alkynyl group contains 1 or 2 carbon-carbon triple bonds.

The term “aryl” as used herein refers to an aromatic, carbocyclic system, e.g., of about 6 to 14 carbon atoms, which can include a single ring or multiple aromatic rings fused or linked together where at least one part of the fused or linked rings forms the conjugated aromatic system. The aryl groups include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, tetrahydronaphthyl, phenanthryl, indene, benzonaphthyl, and fluorenyl.

The term “heterocycle” or “heterocyclic” as used herein can be used interchangeably to refer to a stable, saturated or partially unsaturated 3- to 9-membered monocyclic or multicyclic heterocyclic ring. The heterocyclic ring has in its backbone carbon atoms and one or more heteroatoms including nitrogen, oxygen, and sulfur atoms. In one embodiment, the heterocyclic ring has 1 to about 4 heteroatoms in the backbone of the ring. When the heterocyclic ring contains nitrogen or sulfur atoms in the backbone of the ring, the nitrogen or sulfur atoms can be oxidized. The term “heterocycle” or “heterocyclic” also refers to multicyclic rings in which a heterocyclic ring is fused to an aryl ring of about 6 to about 14 carbon atoms. The heterocyclic ring can be attached to the aryl ring through a heteroatom or carbon atom provided the resultant heterocyclic ring structure is chemically stable. In one embodiment, the heterocyclic ring includes multicyclic systems having 1 to 5 rings.

A variety of heterocyclic groups are known in the art and include, without limitation, oxygen-containing rings, nitrogen-containing rings, sulfur-containing rings, mixed heteroatom-containing rings, fused heteroatom containing rings, and combinations thereof. Examples of heterocyclic groups include, without limitation, tetrahydrofuranyl, piperidinyl, 2-oxopiperidinyl, pyrrolidinyl, morpholinyl, thiamorpholinyl, thiamorpholinyl sulfoxide, pyranyl, pyronyl, dioxinyl, piperazinyl, dithiolyl, oxathiolyl, dioxazolyl, oxathiazolyl, oxazinyl, oxathiazinyl, benzopyranyl, benzoxazinyl and xanthenyl.

The term “heteroaryl” as used herein refers to a stable, aromatic 5- to 14-membered monocyclic or multicyclic heteroatom-containing ring. The heteroaryl ring has in its backbone carbon atoms and one or more heteroatoms including nitrogen, oxygen, and sulfur atoms. In one embodiment, the heteroaryl ring contains 1 to about 4 heteroatoms in the backbone of the ring. When the heteroaryl ring contains nitrogen or sulfur atoms in the backbone of the ring, the nitrogen or sulfur atoms can be oxidized. The term “heteroaryl” also refers to multicyclic rings in which a heteroaryl ring is fused to an aryl ring. The heteroaryl ring can be attached to the aryl ring through a heteroatom or carbon atom provided the resultant heterocyclic ring structure is chemically stable. In one embodiment, the heteroaryl ring includes multicyclic systems having 1 to 5 rings.

A variety of heteroaryl groups are known in the art and include, without limitation, oxygen-containing rings, nitrogen-containing rings, sulfur-containing rings, mixed heteroatom-containing rings, fused heteroatom containing rings, and combinations thereof. Examples of heteroaryl groups include, without limitation, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, azepinyl, thienyl, dithiolyl, oxathiolyl, oxazolyl, thiazolyl, oxadiazolyl, oxatriazolyl, oxepinyl, thiepinyl, diazepinyl, benzofuranyl, thionapthene, indolyl, benzazolyl, purindinyl, pyranopyrrolyl, isoindazolyl, indoxazinyl, benzoxazolyl, quinolinyl, isoquinolinyl, benzodiazonyl, napthylridinyl, benzothienyl, pyridopyridinyl, acridinyl, carbazolyl, and purinyl rings.

The term “thioaryl” as used herein refers to the S(aryl) group, where the point of attachment is through the sulfur-atom and the aryl group can be substituted as noted herein. The term “alkoxy” as used herein refers to the O(alkyl) group, where the point of attachment is through the oxygen-atom and the alkyl group can be substituted as noted herein. The term “thioalkyl” as used herein refers to the S(alkyl) group, where the point of attachment is through the sulfur-atom and the alkyl group can be substituted as noted herein.

The term “hydroxyalkyl” refers to -(alkyl)OH, where the point of attachment is group through the alkyl group and the alkyl groups is defined above.

The term “alkylcarbonyl” or “arylcarbonyl” as used herein refers to the group

in which R is an alkyl or aryl and X′ refers to the leaving group(s), as described below. “Leaving group” refers to the group displaced by the amine in the reactions described herein. This includes esters, acid halides, lactones, anhydride, cyclic anhydrides, or linear polyanhydrides, etc. Some examples are:

The term “optionally substituted” as used herein refers to the base group having one or more substituents including, without limitation, H, halogen, CN, OH, NO₂, amino, alkyl, cycloalkyl, alkenyl, alkynyl, C₁ to C₃ perfluoroalkyl, C₁ to C₃ perfluoroalkoxy, aryl, heterocyclic, heteroaryl, alkoxy, aryloxy, alkylcarbonyl, alkylcarboxy, arylthio, alkylamino, or —SO₂-(optionally substituted C₁ to C₁₀ alkyl).

As referred to herein, the molecular weight of the polyamidopolyamines and non-polymeric amidoamines are measured using either the gel permeation column (GPC) method or by NMR and mass spectrometry, i.e., MALDI-TOF. It is anticipated that the GPC measurements are likely to be most accurate. “Weight average molecular weight” as used herein means the average of the molecular weights of all of the polyamidopolyamines present in a single condensation reaction. The molecular weight ranges cited herein and weight average molecular weights are expected to be understood to be broad enough to cover measurements made by either GPC or mass spectrometry methods or by other acceptable measurement technologies.

The term “molar basis” or “molar ratio” as used herein refers to the molar concentration of polybasic acid to primary amine. For example, where the reaction is between a dibasic acid (1 mole) and a polyamine (2 moles) having at least three primary amine groups, the molar ratio is 1:2. Where a tribasic acid is employed in the condensation reaction with a polyamine having at least three primary amine groups, the molar ratio is 1:3. Where a tetrabasic acid is employed in the condensation reaction with a polyamine having at least three primary amine groups, the molar ratio is 1:4, and so on. This ratio can be reduced to 1:1 when the reaction occurs in the presence of an organic hydroxyl solvent. In some embodiments, excess polyamine allows the reaction mixtures to be fluid. The use of organic hydroxyl solvents accomplishes the same purpose, i.e., reduces viscosity.

If the reaction employs only monobasic acids (“capping”)with primary amine or polyamine, the term “molar basis” is alternatively defined as follows: The moles of monobasic acid are equal to the number of primary amino groups on the polyamine minus at least one (1). For example, when the number of primary amino groups on the polyamine is 2, the moles of monobasic acid is 1. When the number of primary amino groups on the polyamine is 3, the moles of monobasic acid are either 2 or 1. When the number of primary amino groups on the polyamine is 4, the moles of monobasic acid are 3, 2 or 1. When the number of primary amino groups on the polyamine is 5, the moles of monobasic acid are 4, 3, 2 or 1, etc. The molar basis employed in the reaction provides the resulting non-polymeric amidoamine with at least one free primary amino group. The presence of the at least one free primary amino group in the non-polymeric amidoamine provides some degree of antimicrobial activity, which increases with the number of free primary amino groups. Where there are no primary amino groups left in the reactant of this reaction between monobasic acid and primary amine or polyamine, the reactant or composition containing the reactant does not have anti-microbial properties, but the other properties, e.g., defoaming and/or lubricating properties remain.

The term “polybasic acid”, as used in these preparative methods, is an acid composed of two or more C(O)OH groups or derivatives thereof. A C(O)OH derivative includes, without limitation, an ester, anhydride, acid halide, lactone, polyanhydride, or lactam thereof. Among suitable polybasic acids for the methods described herein are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, thapsic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, tartartic acid, malic acid, gluconic acid, citric acid, cysteine, aspartic acid, glutamic acid, mucic acid, or combinations thereof. Additionally, combinations of two or more of these polybasic acids are also useful in the preparative methods for the polyamidopolyamines.

In one embodiment, the molecular weight (MW) of the selected polybasic acid is from about 90 to about 314 MW. In another embodiment, the molecular weight of the selected polybasic acid is from about 104 to about 272 MW. In still other embodiments, the MW is 90, 104, 118, 132, 146, 160, 174, 188, 202, 216, 230, 244, 258, 272, 286, 300, 314 or more, including any numbers between and including any two endpoints of the range selected from this list.

The term “monobasic acid”, as used herein, is an acid composed of one C(O)OH group or derivative thereof. Monobasic acids are useful in the condensation reactions with a primary amine to produce the non-polymeric amidoamines. Alternatively, monobasic acids are useful for terminating the dendrimer reaction to create polyamidopolyamines. In another alternative, the monobasic acids are useful in condensation reactions with other polybasic acids to produce compositions comprising polyamidopolyamines and non-polymeric amidoamines. Suitable monobasic acids for these purposes include, without limitation, acetic acid, propionic acid, butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmetic acid, stearic acid, decylenic acid, stillingic acid, palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, punicic acid, licanic acid, parinaric acid, glycolic acid, lactic acid, methoxyacetic acid, thioglycoloic acid, phenylacetic acid, glucine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, proline, hydroxyproline, threonine, cysteine, tryptophane, arginine, lysine, histidine, gluconic acid, glyceric acid, or combinations thereof. Additionally, combinations of two or more of these monobasic acids are also useful in the preparative methods described herein.

In one embodiment, the molecular weight (MW) of the selected monobasic acid is from about 46 to about 312 MW. In another embodiment, the molecular weight of the selected monobasic acid is from about 74 to about 270 MW. In still other embodiments, the MW is 46, 60, 74, 88, 102, 116, 130, 144, 158, 172, 186, 200, 214, 228, 242, 256, 270, 284, 298, 312 or more, including any numbers between and including any two endpoints of the range selected from this list.

The term “amino group” as used herein means the formula —NRR¹, where in R and R′ are independently H, or a C₁ or C₂ alkyl. In some embodiments, the amino groups are primary, wherein the nitrogen has two reactive hydrogens, e.g., —NH₂. In other embodiments, the amino groups are secondary, e.g., —NHCH₃, wherein the nitrogen has a single reactive hydrogen. In still other embodiments, the amino groups are tertiary, e.g., —N(CH₃)CH₃. Whereever in the formulae and other examples of polyamidopolyamines, the amino group is shown as NH₂, it should be understood to include replacement thereof with secondary or tertiary amino groups by way of alkylation with alkyl halides (alkylation of amines) up to and including quaternary ammonium salts. The term “pendant amino group” is meant to refer to amino groups attached to a polymeric unit, and can repeat at regular intervals or intermittently along the polymer chain, also including terminal amino groups. The term “unreacted amino group” means a primary amino group, NH₂. The amino group can also be converted to a salt with acid(s).

The term “polyamine” as used herein refers to any compound comprising a primary amine (or amino) group. In one embodiment, the polyamine has one or more amino groups. In another embodiment, the polyamine has two or more amino groups. In still other embodiments, the polyamine has at least three primary amino groups. In another embodiment the polyamine has 5 or more primary amino groups.

The term “polyamidopolyamine” as used herein refers to a polymeric compound having at least one primary amino group(s). In one embodiment, the compound has at least two primary amino groups. In another embodiment, the compound has at least three primary amino groups. In still another embodiment, the compound has at least four primary amino groups. When the polyamidopolyamine is one of Formula A through E (as described herein), the number of primary amino groups in the polymer is between 4 and 14. When the polyamidopolyamine is prepared by the sequential (dendrimer) method described herein, the polymer may have more than 14 primary amines, based on the selection of polybasic acid and primary amine employed to generate the polymer. In certain embodiments, these polyamidopolyamine compounds are prepared by the condensation of polyamino compounds with polybasic acids.

The term “non-polymeric amidoamine” as used herein refers to a linear or branched non-polymeric compound having at least one primary amino group(s). In one embodiment, the compound has at least two primary amino groups. In another embodiment, the compound has at least three primary amino groups. In still another embodiment, the compound has at least four primary amino groups. When the non-polymeric amidoamine is one of Formula F (described herein), the number of primary amino groups in the amidoamine is 2. When the non-polymeric amidoamine is one of Formula G, the number of primary amino groups in the amidoamine is 1. In certain embodiments, these non-polymeric amidoamine compounds are prepared by the condensation of polyamino compounds with monobasic acids.

The term “imide” as used herein refers to a compound containing two carbonyl groups bonded to a primary amine, e.g., having the formula below, wherein R, R′ and R″ are independently an alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic group, aryl, heteroaryl, etc :

The term “diluent” or “solvent” as used herein is a hydroxyl containing diluent or solvent. In one embodiment, that diluent is water. In one embodiment, when the hydroxyl containing diluent used in the condensation reactions is water, it is added at the end of the condensation reaction. In other embodiments, water may also be present or added to the various use compositions or concentrates containing the compounds described herein, such as quenching compositions. In another embodiment, the hydroxyl containing diluent is an organic diluent. In embodiments where the organic diluent or solvent participates in the condensation reactions, as described below, it is not removed from the reaction mixture. Among suitable organic diluents are alcohols, polyols, carbitols, CELLOSOLVE™ Solvents (Dow Chemical), or combinations of these four types of diluents. In one embodiment, the organic diluent contains a polyol, such as a glycol. One such exemplary diluent contains a polyalkylene glycol. In another embodiment, the hydroxyl containing diluent contains ethylene glycol or diethylene glycol. In another embodiment the diluent comprises triethanolamine. In still another embodiment, the diluent contains N,N,N′,N′-tetrakis (2-hydroxypropyl) ethylenediamine (also known at tetra(2-hydroxypropyl) ethylenediamine). Another diluent component is glycerin. Still other diluents may be prepared by combinations of any two or more of the above noted hydroxyl-containing diluents. One of skill in the art may readily select such diluents from among the many diluents or solvents available.

The term “water-soluble” as used herein refers to the ability of a chemical component to combine with, disperse, or be emulsified, in water. Desirably, the polyamidopolyamines and/or non-polymeric amidoamines and compositions containing them as described herein substantially dissolve in water. More desirably, the term “water-soluble” refers to a compound or composition that has 100% dissolution in water.

By “water-soluble acid” is meant an acid which when added to the compositions described and used herein enhances the water solubility of the other components, particularly the polyamidopolyamine, the amidopolyamines (from monobasic acid), and/or the non-polymeric amidoamines. In one embodiment, the water soluble acid is phosphoric acid. In another embodiment, the water soluble acid is acetic acid or glycolic acid or lactic acid. In still other embodiments, combinations of these water soluble acids are used. Other acids which enhance water solubility of the compositions described herein are intended to be incorporated by this term.

The term “antimicrobial” as used herein means a agent, component or composition that is destructive to, or inhibits the growth of, microorganisms (bacteria, virus, fungus, etc.) which come into contact with the antimicrobial agent, component or composition.

The term “bioresistance” as used herein means that the composition, agent or component does not support the growth of microorganisms on or in a substrate (e.g., a surface or fluid) treated with or containing the composition, agent or component.

The term “metal” as used herein refers to any commercial metal that requires use of a industrial fluid for its treatment or manufacture, e.g., metal rolling fluids, quenching fluids, hydraulic fluid, and the like. In one embodiment, the tem refers to any metal, metal alloy or metal substrate that can be heated to a high temperature, e.g., up to 1600° C., requiring cooling (e.g., quenching) in a fluid. In one embodiment, the metal contains only one metallic element. In another embodiment, the metal contains more than one metal element, i.e., a metal alloy. For example, the metal may contain one or more of aluminum, iron, manganese, copper, silicon, sulfur, phosphorus, chromium, cobalt, columbium, molybdenum, nickel, titanium, tungsten, vanadium, zirconium, lead, tin, or zinc, among others. Specific examples of metals that can be treated with the compositions described herein include those described in the “Handbook of Hydraulic Fluid Technology”, 2^(nd) ed., Totten, CRC Press, 2011, which is herein incorporated by reference. In certain embodiments, specific examples of metals that can be treated with certain quenching compositions described herein include those described in “The Heat Treater's Guide”, American Society for Metals, 1982, which is hereby incorporated by reference. Employing the methods and system described herein, the resultant metal is not negatively impacted, i.e., it retains its desired porosity ductility, strength such as an excellent strength-to-weight ratio, weight, shape, corrosion resistance mechanical properties, such as good thermal electrical conductivity, high temperature resistance, hardness, wear resistance, durability, and dimensional stability, among others.

The phrase “in contact with”, when utilized to refer to a surface's interaction with the compositions described herein, includes any point of contact of the surface with the composition. Such contact includes, without limitation, application of the composition to the surface (e.g., metal, polyurethane, or fibrous surfaces, e.g., cotton or paper, etc.) using conventional techniques. Such conventional techniques include, without limitation, coating, spraying, contact rolling, squeegeeing, dipping, brushing, flooding, or immersion application techniques. In one embodiment, the surface is contacted with the composition prior to further manipulation of the surface. In another embodiment, the surface, e.g., metal, is contacted with the composition during use of the surface, e.g., metal in the desired method, e.g., rolling, stamping, etc.

The term “number” as used throughout this specification and particularly in reference to molecular weights means a whole number or any fraction between two other whole numbers, when applicable. In certain embodiments, a fractional number referring to molecular weight means molecular weights of isotopes or molecular weight averages.

By “additively” as used herein to define substituents of a formula, is meant that the values of the referenced subscripts, e.g., x+y+z equal a number between, and including, two specified endpoints of the range. Each subscript may be the same or a different number as other subscripts forming the sum, provided that the sum of all subscripts is between the lowest and highest point in the range, including the endpoints of the range.

By “independently” as used herein to define substituents of a formula, means that each substituent may be any one of a following list of identified substituents, independent of other substituents in a group. For example, “R1 and R2 are independently, alkyl, aryl or alkenyl”, means that R1 and R2 may be the same or different but must be one of alkyl, aryl or alkenyl.

Various embodiments in the specification are presented using “comprising” language, which is inclusive of features in addition to the specifically recited features or steps. Under other circumstances, a related embodiment is also intended to be interpreted and described using “consisting of” or “consisting essentially of” language. The words “consist”, “consisting”, and its variants, are to be interpreted to exclude features in addition to those features specifically recited, or to include only additional features of minor significance.

It is to be noted that the term “a” or “an” refers to one or more. As such, the terms “a” (or “an”), “one or more,” and “at least one” are used interchangeably herein.

As used herein, the term “about” means a variability of 10% from the reference given, unless otherwise specified.

Unless defined otherwise in this specification, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and by reference to published texts, which provide one skilled in the art with a general guide to many of the terms used in the present application.

The Compositions

The compositions described herein contain one or more of the following components, or admixtures of various of these components. In one embodiment, the compositions described herein contain a polyamidopolyamine, which is a linear, cyclic, branched or crosslinked amide comprising a primary amino group. In certain embodiments the polyamidopolyamines comprises one or more, two or more, three or more or 14 or more amino groups, as described throughout this specification. In one embodiment, the compositions of polyamidopolyamine or mixtures thereof are produced by the reaction of a polybasic acid and polyamine in the presence of an optional organic diluent as described below. In certain other embodiments, the method of making the polyamidopolyamine and mixtures thereof involves repeated cycles of condensation reactions as described in more detail below. In still other embodiments, the method of making the polyamidopolyamine or a composition comprising it involves a condensation reaction employing at least one polybasic acid and at least one polyamine.

In additional embodiments, the compositions described herein contain a non-polymeric amidoamine, which is a linear or branched amide comprising a primary amino group. In certain embodiments the non-polymeric amidoamine comprises one or more, two or more, three or more amino groups, as described throughout this specification. In one embodiment, the compositions of non-polymeric amidoamine or non-polymeric amide or mixtures thereof are produced by the reaction of a monobasic acid and primary amine in the presence of an optional organic diluent as described below. In still other embodiments, the method of making a composition comprising a non-polymeric amidoamine and a polyamidopolyamine involves a condensation reaction employing at least one polybasic acid, at least one monobasic acid and at least one polyamine or primary amine.

The composition, in still another embodiment, contains a mixture of multiple polyamidopolyamines and/or non-polymeric amidoamines of different formulae. In certain embodiments, the composition may also contain polyamidoamines and/or polyamidopolyamides or non-polymeric amides in admixture with these polyamidopolyamines and/or non-polymeric amidoamines. In yet a further embodiment, the composition may contain a polyamidopolyamine that further comprises an imide group. Still other embodiments of the composition contain a mixture of any number of the polyamidopolyamines, with or without imide groups, and with unreacted polyamine. Still other embodiments of the composition contain a mixture of any number of the non-polymeric amidoamines, and/or non-polymeric amides, and with unreacted polyamine. In still other embodiments, the composition may contain multiple different non-polymeric amidoamines, multiple different non-polymeric amides, multiple different unreacted primary amines, multiple different monobasic acids, or any combination thereof

These compositions as described herein have a variety of uses. Depending upon its complete formulation, the composition containing the polyamidopolyamine and/or non-polymeric amidoamine has antimicrobial properties. In another embodiment the composition containing the polyamidopolyamine and/or non-polymeric amidoamine has bioresistant properties. In another embodiment the composition containing the polyamidopolyamine and/or non-polymeric amidoamine has low-foaming, defoaming or anti-foaming properties. In another embodiment the composition containing the polyamidopolyamine and/or non-polymeric amidoamine has lubricating and/or load carrying properties. In still other embodiments, the same composition has bioresistant and defoaming properties. In yet other embodiments, the same composition has bioresistant and lubricant properties. In a further embodiment, the same composition has bioresistant, lubricant and defoaming or anti-foaming properties. In another embodiment, the same composition has antimicrobial properties. In still other embodiments, the same composition has antimicrobial and defoaming properties. In yet other embodiments, the same composition has antimicrobial and lubricant properties. In a further embodiment, the same composition has bioresistant, lubricant, defoaming, deaeration, or anti-foaming properties.

In one embodiment, the composition is provided as a concentrate. In another embodiment, the composition comprises water or any organic diluent. In another embodiment, the composition comprises an organic hydroxyl-containing diluent. These compositions can be provided as additives containing the described polyamidopolyamines for a variety of industrial fluids and uses. Alternatively, the compositions are themselves industrial fluids based upon the inclusion of other components. For example, the compositions, depending upon the other components can be lubricants, metal working fluids, metal cleaning fluids, other industrial cleaning fluids, metal drawing fluids, metal stamping fluids, metal rolling fluids, hydraulic fluids, metal quenching fluids, coatings for protecting surfaces, such as polyurethane surfaces, fibers, paper, paints, fluids for use in paper making, fluids to decrease or eliminate biofilms, and others, in which the polyamidopolyamines are present in amounts sufficient to add one or more desired characteristics to the final composition. In other embodiments, the compositions are process fluids that are dilutable in water. See also, the uses described in detail in the Use section below.

The Polyamidopolyamines and/or Non-Polymeric Amidoamines and Methods for Preparing Them

In one embodiment, a polyamidopolyamine present in a composition of this invention as described herein has the following Formula A, in a 2:1 molar ratio of polyamine to dimer acid:

According to this formula, each polybasic acid is a dimer acid. Each polyamine is independently a primary amine, such as a diamine, a triamine, or a tetraamine or an amine comprising 3 or more free amino groups. The two subscripts a and a′ are independently 1 or 2; and the subscript b is 0, 1 or 2. The subscript r represents a number between 2 to about 10, including both endpoints of the range. The value of r can thus be 2, 3, 4, 5, 6, 7, 8, 9 or 10 including either of the included endpoints of the range.

In another embodiment, for a 1:1 molar ratio of polyamine to dimer acid, a compound of Formula A′ exists along with a compound of Formula A. Formula A′ is:

In one embodiment of this formula, (a) is a number from 1 to 4. For example, where the polyamine has 3 amino groups, a=3−2=1. Where the polyamine has 4 amino groups, a=4−2=2. Where the polyamine has 6 amino groups, a=6−2=4, and so on.

In another embodiment, a polyamidopolyamine present in a composition of this invention as described herein has the following Formula B,

According to this formula, each polybasic acid is a trimer acid. Each polyamine is independently a primary amine, such as a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups. The four subscripts a, c, d and e are each independently 1 or 2; and the subscript b is 0, 1 or 2. The subscript r represents a molar percentage of different polyamines and different polybasic acids, e.g., 75% of polyamine A plus 25% of polyamine B with 50% polybasic acid C and 50% polybasic acid of D. The r is thus a number between 3 to about 10, including both endpoints of the range. The value of r can thus be at least 3, 4, 5, 6, 7, 8, 9, or 10 including the included endpoints of the range.

In another embodiment, a polyamidopolyamine present in a composition of this invention as described herein has the following Formula C:

According to this formula, each polybasic acid is a tetrabasic acid. Each polyamine is independently a primary amine, such as a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups. The four subscripts a, c, d, and e are independently a number 1 or 2; and the subscript b is a number 0, 1 or 2. The subscript r represents a number between 4 and about 10 (e.g., at least 4, 5, 6, 7, 8, 9 or 10, including both endpoints of the range).

In another embodiment, a polyamidopolyamine, which contains at least one imide group is present in a composition of this invention. See for example Formula E, described in detail at paragraph 00122 herein.

In a more specific embodiment, the polyamidopolyamine of the composition has the following Formula D shown below.

Compounds according to this formula are those in which R¹, R², R³, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently, H, methyl, ethyl, propyl or butyl and R⁴, R⁴′, and R⁴″ are independently methyl, ethyl, propyl or butyl. The subscripts x, y, z, and x′, y′, z′, and x″, y″, and z″ are all defined additively, that is, x+y+z equals a number from 3 to about 90; x′+y′+z′ equals a number from about 3 to about 90; and x″+y″+z″ equals a number from 3 to about 90. This additive subscript value x, y, and z, or x′, y′ and z′, or x″, y″ and z″ includes both endpoints of the range and is selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

The formula subscript, n, is a number between 1 to 14, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14 including the endpoints of the range. The formula subscript, m, represents a number selected independently of the value of n, and is also a whole number between 1 to 14, including e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14. The formula subscript r represents a number between 2 to about10, including both endpoints of the range. The value of r can thus be at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 and including the endpoints of the range.

In one embodiment of a polyamidopolyamine of Formula D, R¹, R², R³, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are each methyl; R⁴ is ethyl; and n and m are each 4. The additive formula x+y+z is about 5; x′+y′+z′ is about 5; and x″+y″+z″ is about 5. The compound formed when r is 2 has four primary amine groups. The compound formed when r is 3 has 5 primary amine groups. The compound formed when r is 4 has six primary amine groups. The compound formed when r is 5 has 7 primary amino groups.

Still other polyamidopolyamines described herein are shown below and labeled as Formula I through V. In one embodiment, the polyamidopolyamine is of the Formula I shown below. The subscripts x, y, z, and x′, y′, z′, and a, b, and c are all defined additively, that is, x+y+z equals a number from 3 to about 90 (see para 0083); x′+y′+z′ equals a number from about 3 to about 90; and a+b+c equals a number from 3 to about 90. In another embodiment, the polyamidopolyamine is of the Formula II shown below, wherein x, y, z, x′, y′, and z′ are defined additively, that is, x +y +z equals a number from 3 to about 90 (see para 0083); and x′+y′+z′ equals a number from about 3 to about 90 (see para 0083). In another embodiment, the polyamidopolyamine is of the Formula III shown below, wherein x, y, z, and x′, y′, z′, and a, b, and c are additively 3 to about 90 (see para. 0083). In another embodiment, the polyamidopolyamine is of the Formula IV shown below, wherein x, y, z, x′, y′, z′, a, b, and c are additively 3 to about 90, that is, x+y+z equals a number from 3 to about 90 (see para 0083); x′+y′+z′ equals a number from about 3 to about 90; and a+b+c equals a number from 3 to about 90 (see para. 0083). In another embodiment, the polyamidopolyamine is of the Formula V shown below, wherein x, y, z, x′, y′, z′, a, b, and c are defined the same as for Formula IV.

In some embodiments, these polyamidopolyamines are suitable for use in quenching compositions, among other uses.

In one embodiment, a non-polymeric amidoamine present in a composition of this invention as described herein has the following Formula F:

According to this Formula F, the subscripts x, y and z are defined additively, that is the sum of x+y+z equals a number between 3 to about 90, including both endpoints of the range, and as described in para. 0083. Also according to this formula, the monobasic acid is a carboxylic acid; and R¹ is C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl, as defined herein. Thus, R¹ can be a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀ or C₁₁ alkyl or substituted alkyl. In one embodiment of a non-polymeric amidoamine of Formula F, R¹is methyl; and x+y+z equals about 5 or 6. In this embodiment, the molar ratio of monobasic acid to primary amine is 1:1.

In another embodiment, a non-polymeric amidoamine present in a composition of this invention as described herein has the following Formula G:

According to this formula, x, y, and z, additively, equal a number between 3 to about 90, including both endpoints of the range (see para. 0083). According to this formula, R¹ and R² are, independently, C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl. Thus, R¹ or R² can individually be a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀ or C₁₁ alkyl or substituted alkyl. According to this formula, the molar ratio of acid to triamine is 2:1.

Still other polyamidopolyamines and/or non-polymeric amidoamines and/or compositions comprising one or both such compounds as described herein may be defined by their method of preparation. Thus in one embodiment, the polyamidopolyamine and/or polyamidoamine having a molecular weight of about 500 to about 100,000 and comprising at least one, or at least two, or at least three or at least 4 or more primary amino groups or a composition containing one or a mixture of multiple polyamidopolyamines is prepared by a condensation reaction between a polybasic acid and a polyamine.

In one embodiment, the composition or compound is prepared by a method comprising condensing (i) a polyamine comprising three primary amino groups and (ii) a C₃ to C₁₆ polybasic acid or derivative thereof. In one embodiment, this reaction occurs in the presence of an organic hydroxyl-containing diluent. In another embodiment, the polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising at least four primary amino groups and/or a composition containing it is prepared by a method comprising condensing (i) two polyamines comprising three or more primary amino groups and (ii) a C₃ to C₁₆ polybasic acid or derivative thereof. In one embodiment, this reaction occurs in the presence of an organic hydroxyl-containing diluent.

In another embodiment, the polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising four or more primary amino groups and/or a composition containing it is prepared by a method comprising condensing (i) a polyamine comprising at least three primary amino groups and (ii) two C₃ to C₁₆ polybasic acids or derivative thereof. In still another embodiment, this reaction occurs in the presence of an organic hydroxyl-containing diluent.

In yet another embodiment, the polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising multiple primary amino groups and/or a composition containing it is prepared by a method comprising condensing (i) a polyamine comprising three primary amino groups, (ii) a polyamine comprising two primary amino groups, and (iii) a C₃ to C₁₆ polybasic acid or derivative thereof. In still another embodiment, this reaction occurs in the presence of an organic hydroxyl-containing diluent.

Still other combinations of selected polybasic acids and selected polyamines or primary amines comprising one or more amino groups may participate as reactants in a suitable condensation reaction to produce the polyamidopolyamines. One of skill in the art given the teachings of this specification can readily select other polybasic acids and polyamines.

In still another method, a composition comprising a polyamidopolyamine having a molecular weight of greater than about 100,000 and comprising multiple primary amino groups and/or a composition containing it is prepared by sequential condensation reactions (i.e., a dendrimer process). According to this method, a polybasic acid is reacted with a polyamine and an optional hydroxyl-containing solvent to produce a first polyamidopolyamine as a reaction product. The polyamidopolyamine reaction product of the first reaction is then itself reacted with the same or different a polybasic acid and an optional hydroxyl-containing solvent to produce another polyamidopolyamine as a subsequent polyamidopolyamine reaction product. Additional sequential condensation reactions are performed by reacting the polyamidopolyamine reaction product of each preceding condensation reaction with the same or different polybasic acid and an optional hydroxyl-containing solvent for a selected number of iterations.

The reaction sequence may be terminated by addition of a monobasic acid or polybasic acid, by a condensation reaction or a salt reaction, or by neutralization with an acid, preferably a water soluble acid as described above. This termination can occur when the composition demonstrates a desired characteristic selected from anti-foaming, low-foaming, defoaming, lubricity, bioresistance, antimicrobial activity or any desired combination of these characteristics.

The polyamines and polybasic acids used in the methods described above, including the sequential (dendrimer) reaction method, may be selected from among known compounds or those specifically identified herein. In the sequential reaction, the polyamines and polybasic acids may be the same in each sequential reaction or different. The reactants for any of the above methods can include any of the polybasic acids comprising two C(O)OH groups or derivatives thereof, as identified above. Some of the free amino groups can be further terminated to amide (salts) with cyclic anhydride (such as succinic anhydride or glutamic anhydride) to cap amino groups at a temperature which is below condensation reaction temperature. Such a temperature is between 90 and 95° C.

In still other embodiments, the non-polymeric amidoamine having a molecular weight of about 290 to about 5000 and comprising at least one, or at least two, or at least three or more primary amino groups or a composition containing one or a mixture of multiple non-polymeric amidoamines and optionally one or more of a mixture of non-polymeric amides as described herein is prepared by a similar condensation reaction between a selected monobasic acid and a primary amine, or by condensation reactions between multiple monobasic acids and one or multiple amines or polyamines, in a manner similar to the condensation reactions described above for the polyamidopolyamine-containing compositions.

In yet another embodiment, compositions comprising mixtures of polyamido-polyamine(s) and non-polymeric amidoamine(s), with or without certain amounts of the free reactants, are prepared by condensation reactions employing a polybasic acid, a monobasic acid and one or more polyamines or amines, in a manner similar to that described herein.

A large number of available polyamines or primary amines are useful in all of these described methods.

In one embodiment of the preparative methods described above, a suitable polyamine is triaminononane. In another embodiment, the method uses a polyamine of the formula:

In this formula, R¹, R³, and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R⁴ and R⁶ are independently methyl, ethyl, propyl, or butyl; and a, b and c are additively a number between 0 to about 90, including both endpoints of the range (see para. 0083).

A more specific suitable polyamine for use in the preparative methods is:

In this polyamine, s, t and u are additively a number between 3 to about 90, including both endpoints of the range (see para. 0083).

Still another suitable polyamine has the formula:

For this polyamine, R¹ is H, methyl, ethyl, propyl or butyl; R², R³, and R⁴ are, independently, methyl, ethyl, propyl, or butyl; and e and f are additively a number between 0 to about 90, including both endpoints of the range (see para. 0083).

A more specific polyamine has the formula:

NH₂CH(CH₃)CH₂—(O—CH₂CH₂)_(g)—(O—CH₂CH(CH₃))_(h)—(O—CH₂CH(CH₃))—NH₂

wherein g and h are additively a number between 0 to about 90, including both endpoints of the range (see para. 0083).

Still another suitable polyamine is of the formula:

In this formula, R¹, R³, R⁵ and R⁷ are independently H, methyl, ethyl, propyl or butyl; R², R⁴, R⁶ ,and R⁸ are independently methyl, ethyl, propyl, or butyl; and w, j, k and m are additively a number between 0 to about 90, including both endpoints of the range (see para. 0083).

Another more specific polyamine has the formula:

In which h, n, o and p are additively a number between 4 to about 90, including both endpoints of the range (see para. 0083).

Still another suitable polyamine for use in these methods has the formula:

In this formula, R¹, R³, and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R⁴, and R⁶ are methyl, ethyl, propyl, or butyl; and a′, b′ and c′ are additively a number between 0 to about 90, including both endpoints of the range (see e.g., para 0083). Still another more specific polyamine has the formula:

in which wherein e′, f′ and g′ are additively a number between 3 to about 90 (see, para 0083). A specific polyamine under this formula is marketed as Jeffamine® T403 (Huntsman Corporation) and is used in the Examples below.

These methods of preparing the compositions and compounds described herein involve in one embodiment, performing the condensation reaction with the selected reactants of polyamine(s) and polybasic acid(s) and/or monobasic acid(s) in the presence of water (which is removed during the course of the reaction) or a hydroxyl-containing organic diluent, described above. In certain embodiments, the methods include the steps of adding an organic hydroxyl-containing diluent or solvent at the initiation of the reaction. In other embodiments, the methods include adding water or an organic hydroxyl-containing diluent or solvent at the end of the reaction to adjust viscosity of the composition. In still other embodiments of these preparative methods, diluent is added at both points of the reaction. In the condensation reactions identified herein, the organic hydroxyl component acts as a diluent when added at the end of the reaction to control viscosity of the resulting polyamidopolyamine and/or non-polymeric amidoamine-containing compositions. In another embodiment, the organic hydroxyl component acts as a reactive intermediate in the condensation reaction (i.e., forms an ester). This intermediate is converted to the amide during the reaction, regenerating the organic hydroxyl compound, and remains in the final product.

In one embodiment of the preparative methods, the mole ratio of the polybasic acid to polyamine is the ratio 1: (1×), wherein X is the number of C(O)OH groups in the polybasic acid. In one embodiment, in a reaction in which the polybasic acid is a dibasic acid, the ratio of polybasic acid to polyamine is about 1 to about 2. In one embodiment of the preparative methods, the mole ratio of the tribasic acid to polyamine is about 1 to about 3. In one embodiment of the preparative methods, the mole ratio of the tetrabasic acid to polyamine is about 1 to about 4, and so on. In another embodiment, the mole ratio of the polybasic acid to the polyamine is about is about 1:1. This ratio can be used when the reaction is conducted in the presence of an organic hydroxyl solvent, or without such solvents. For example, the mole ratios of polybasic acid to polyamine can be 4 to 5, 9 to 10, 24 to 25, etc. Where a monobasic acid is a reactant with a polyamine, the molar ratio or molar basis is as described herein in paragraph 00125.

Generally, the temperature of the condensation reactions is between about 150° C. to about 175° C. or between about 160° C. to about 165° C. In another embodiment, the temperature is about 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174 or about 175° C. The reactions can take place from 1 to 24 hours. In one embodiment, the reactions take place for about 8 hours. In other embodiments, the reactions take place for between 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 hours.

In certain embodiments, the compositions resulting from these preparative methods can contain one or more of a polyamidopolyamine, which is a linear, cyclic, branched or crosslinked amide containing at least one or more primary amine groups; one or more of a non-polymeric amidoamine, which when monobasic acid is used is a linear or branched amide containing at least one or more primary amine groups; a polyamidopolyamine having one or more imide groups; a mixture of any or multiple of these polyamidopolyamine(s) or imides or non-polymeric amidoamines; or a mixture of any of these compounds with some unreacted reactants, such as amines, diluent, acids, etc.

There is a small possibility that the composition comprising a polyamidopolyamine may contain a mixture of imide-containing compounds with no primary amine. When polybasic acid carboxyls are in the 1, 2 and or 1, 3 positions, imide formation can result depending on reaction conditions. One exemplary imide-containing polyamidopolyamine is shown in the following Formula E, wherein t is a whole number from 1 to about 5:

Michael addition can also result by primary amine addition across unsaturation of double bonds in conjugation with carbonyl groups of the polybasic acid such as maleic, itaconic, or citraconic acids, among others.

Other Characteristics of the Compounds and/or Compositions Containing Them

In certain embodiments, the polyamidopolyamine of these Formulae A through D comprise from 4 to 14 amino groups. In certain embodiments, the non-polymeric amidoamines of these Formulae F and G comprise from 1 to 3 amino groups. Polyamidopolyamine reaction products of the dendrimer or sequential reactions described may have more than 14 primary amino groups, depending upon the selection of polybasic acid and polyamines in the reaction. In some embodiments, the number of primary amine groups in the resulting polyamidopolyamine is calculated as (# primary amines in the selected polyamine −1)×the number of acid groups in the polybasic acid. For example, the reaction of a 2:1 mole ratio of polyamine with 3 amino groups with a dimer acid results in the number of free amino groups in the polyamidopolyamine including ((3−1)×2) or 4 amino groups, as one structure, among others.

In other embodiments, the number of primary amine groups in the non-polymeric amidoamine is calculated as (# primary amines in the selected polyamine −1)×the number of acid groups in the monobasic acid. For example, the reaction of a polyamine having 3 primary amine groups with a monobasic acid in the reactions described herein produces a non-polymeric amidoamine having (3−1)×1 or 2 primary amine groups etc.

In one embodiment, the polyamidopolyamine has a molecular weight (MW) of between about 500 to about 100,000, including all numbers therebetween and including the endpoints of the range. In certain embodiments, the polyamidopolyamine of these compositions can have MW of at least 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 6000, 7000, 8000, 9000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000 and up to 100,000 including all numbers between any two endpoints of the range. In certain embodiments, in which the method of making the polyamidopolyamine involves repeated cycles of reactions as described below, the polyamidopolyamine compound can have MW of greater than 100,000.

In one embodiment, the non-polymeric amidoamine has a molecular weight (MW) of between about 290 to about 5000, including all numbers therebetween and including the endpoints of the range. In certain embodiments, the non-polymeric amidoamine of these compositions can have MW of at least 290, 390, 490, 590, 690, 790, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and up to 5000. In certain embodiments, the non-polymeric amidoamine compound can have MW of greater than 5000.

In other embodiments, the polyamidopolyamine and/or non-polymeric amidoamine and/or the composition containing that polyamidopolyamine and/or non-polymeric amidoamine is water-soluble. In another embodiment, the polyamidopolyamine and/or non-polymeric amidoamine and/or the compositions containing one or both of them is water dispersible. In another embodiment the composition contains a water soluble acid as defined above to enhance water solubility. Another characteristic of certain polyamidopolyamines is that it is non-shearing in water.

Polyamidopolyamines and/or non-polymeric amidoamines and the compositions described herein are further defined as having a cloud point (i.e., inverse solubility) of between about 25° C. to 82° C. (or 77° F. to 180° F.) in water. Suitable cloud points for these compositions range from about 25° C. to about 82° C., i.e., from 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 73, 80 to 82° C. including any degree between any two of these values. However, some embodiments of the compounds or compositions described herein form cloud points (i.e., appear cloudy) at ambient temperature, i.e., 25° C. These embodiments can be made clear by further cooling.

In one embodiment, the polyamidopolyamine and/or non-polymeric amidoamine desirable for use in these compositions and the compositions them have low-foaming properties. In other embodiments, the polyamidopolyamine and/or non-polymeric amidoamine and/or the composition containing the polyamidopolyamine and/or non-polymeric amidoamines have non-foaming properties. In still other embodiments, these compositions have defoaming properties and the capability of releasing entrained air.

In still other embodiments the polyamidopolyamine and/or non-polymeric amidoamine and/or the compositions them has lubricating properties. In still other embodiments the polyamidopolyamine and/or non-polymeric amidoamine and/or the compositions containing them has a pH of about 8, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0, 10.2, 10.4, 10.6, 10.8, 11.0, or any number therebetween. In still other embodiments the polyamidopolyamine or the composition has bioresistant or antimicrobial properties, due either to the free primary amine groups of the polyamidopolyamine, or optionally to any added antimicrobial component added to the composition to enhance this characteristic. In still other embodiments the non-polymeric amidoamine or the composition containing it has bioresistant or antimicrobial properties, due either to the free primary amine groups of the amidoamine, or optionally to any added antimicrobial component added to the composition to enhance this characteristic.

Uses of the Polyamidopolyamines and/or Non Polymeric Amidoamines and/or Compositions Containing Them

The polyamidopolyamines and/or non-polymeric amidoamines and/or compositions containing one or both such components as described herein can be used to introduce multiple characteristics of lubricity, bioresistence, anti/low/no-foaming or antimicrobial activity to a variety of industrial compositions in need of one or more of those features. Alternatively the compositions containing the polyamidopolyamines and other reaction products generated by the methods may themselves be employed as the additives to other compositions. In still other embodiments, a variety of different additional components may be admixed with the compositions containing the polyamidopolyamines and/or non-polymeric amidoamines to create a variety of different use compositions.

When employed as an additive to other known compositions, e.g., quenchants, lubricants, coatings, etc, it is anticipated that the present polyamidopolyamine and/or non-polymeric amidoamine—containing compositions will be employed to replace multiple components currently in use. In one embodiment, a composition described herein can be used simultaneously for its characteristics as both a lubricant and a defoamer, thereby replacing two components with a single component. Similarly, a composition described herein which has bioresistance or antimicrobial characteristics, as well as defoaming and/or lubricity characteristics may replace three other components in a suitable composition.

Based upon its intended use, or when used as a concentrate, the composition can contain from 0.5 up to about 40% of the polyamidopolyamine or non-polymeric amidoamine or a combination of both. In one embodiment, the composition contains at least 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,30,31, 32, 33, 34, 35, 36, 37, 38, 39 or at least 40%, including any whole or fractional percentages between any two of these values.

The remainder of the concentrate, in one embodiment, can be formed by certain selected additional components described in detail below. Such additional components are selected based upon the use of the resulting composition containing the polyamidopolyamine. In certain embodiments, the composition is dissolved in a hydroxyl-containing diluent. In one embodiment, the concentrate is diluted with in a hydroxyl-containing diluent to form a composition which contains about 60 to about 99% w/w, i.e., 60, 65, 70, 75, 80, 85, 90, 95 to about 99% w/w or numbers there between, of hydroxyl-containing diluent. The hydroxyl-containing diluent may be included in the composition for its intended use, thereby permitting use of the product by the customer without addition of further diluent. Alternatively, diluent is present in the composition in sufficient amounts to provide a stable solution for transportation and storage, if the composition is intended to be further diluted by the customer prior to use.

In still other embodiments, these compositions described herein can be used in aqueous or non-aqueous systems, emulsion systems, etc. In some embodiments, the composition is soluble or dispersible in hydrophobic media, e.g., liquids such as mineral oil. The compositions can also become the discontinuous phase in water when emulsifiers are added to the compositions. The emulsifiers, such as fatty acids, can form soaps which emulsify the polyamidopolyamine and/or non-polymeric amidoamines.

Depending upon the intended use of the composition, a variety of additional components may form part of the composition containing the polyamidopolyamine and/or non-polymeric amidoamine described herein. Whatever use for which the composition is intended, such compositions containing the above polyamidopolyamines and/or non-polymeric amidoamines has a pH of between about 8 to about 11, i.e., a pH of 8.0, 8.5, 9.0, 9.5, 10.0, 10.5 and 11, including any fractional pH value between any two endpoints of the range from 8 to 11.

In general, when use as a defoamer, the polyamidopolyamines and/or non-polymeric amidoamines and/or compositions containing them can desirably replace silicone defoamers. It is anticipated that as a defoamer additive, the compositions or the compounds isolated therefrom may be use at a concentration of between about 0.1 to 0.5% by weight of the resulting use composition, e.g., metal working fluid. This range includes the endpoints of the range, e.g., the present polyamidopolyamine and/or non-polymeric amidoamine—containing compositions can be added at e.g., 0.1, 0.2, 0.3, 0.4 and 0.5% by weight of the resulting use composition.

When used primarily as an additive for its anti-microbial/bioresistant characteristics, it is anticipated that the compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines will be used at a concentration of between about 1 to about 3% by weight of the resulting use composition, e.g., a paint or polyurethane coating fluid. This range includes the endpoints of the range, e.g., the present polyamidopolyamine compositions can be added at e.g., 1.0, 1.3, 1.5, 1.7, 2.0, 2.2, 2.4, 2.6, 2.7, and 3.0% by weight of the resulting use composition. Most desirably, the compositions can be used as a formaldehyde-free anti-microbial, or as an adjuvant to other biocides and fungicides.

When used primarily as an additive for its lubricant characteristics and optionally its bioresistant/antimicrobial characteristics, it is anticipated that the compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines will be used at a concentration of between about 5 to about 30% by weight of the resulting use composition, e.g., a lubricating fluid that does not degrade in the presence of a microorganism. This range includes the endpoints of the range, e.g., the present polyamidopolyamine compositions can be added at e.g., 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30% by weight of the resulting use composition.

In another embodiment, the composition comprising the polyamidopolyamine and/or non-polymeric amidoamines can be used as a quenchant that also optionally provides bioresistance and defoaming properties, when the use composition is metal heat quenching fluid. Suitable quenchants and other quenching components may be selected from among many known in the art. In this embodiment, it is anticipated that the compositions comprising the polyamidopolyamines will be used at a concentration of between about 10 to about 30% by weight of the resulting use composition, and can replace or work in tandem with another quenchant, while also replacing one or more typical quenching additives for lubricity, bioresistance and/or foam control. Compositions containing non-polymeric amidoamines are anticipated to work with the polyamidopolyamines in this context, or as additives to other known quenchant formulations. See, for example, U.S. Pat. Nos. 8,764,914; 4,486,246; 4,528,044; 4,381,205; and 4,404,044 which describe some examples of known quenching fluids.

Thus, in certain embodiments of the heat treating (e.g., quenching) compositions described herein, the polyamidopolyamine comprises a pendent amino group. Polyamidopolyamines useful in these heat treating compositions include those described in U.S. 62/147,840, and throughout this specification, e.g., Formula I-V, herein, as well as those described as follows:

In one embodiment, the polyamidopolyamine is of the Formula I shown above. The subscripts x, y, z, and x′, y′, z′, and a, b, and c are all defined additively, that is, x+y+z equals a number from 3 to about 90 (see para 0083); x′+y′+z′ equals a number from about 3 to about 90; and a+b+c equals a number from 3 to about 90.

In another embodiment, the polyamidopolyamine is of the Formula II shown above, wherein x, y, z, x′, y′, and z′ are defined additively, that is, x+y+z equals a number from 3 to about 90 (see para 0083); and x′+y′+z′ equals a number from about 3 to about 90 (see para 0083).

In another embodiment, the polyamidopolyamine is of the Formula III shown above, wherein x, y, z, and x′, y′, z′, and a, b, and c are additively 3 to about 90 (see para. 0083).

In another embodiment, the polyamidopolyamine is of the Formula IV shown above, wherein x, y, z, x′, y′, z′, a, b, and c are additively 3 to about 90, that is, x+y+z equals a number from 3 to about 90 (see para 0083); x′+y′+z′ equals a number from about 3 to about 90; and a+b+c equals a number from 3 to about 90 (see para. 0083).

In another embodiment, the polyamidopolyamine is of the Formula V shown above, wherein x, y, z, x′, y′, z′, a, b, and c are defined the same as for Formula IV.

In yet another embodiment, the non-polymeric amidoamines useful in these heat treating compositions include those described in U.S. 62/147,840, as well as those described as Formulae F and G described herein and as follows.

Exemplary non-polymeric amidoamines have the formula:

wherein x, y, and z are additively 0 to about 87, including all numbers within that range including the endpoints of the range (see para. 0083), and R′ is C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl (see the range defined in para 0083); or

the formula:

wherein x, y, and z are additively a number between 0 to about 87, including the endpoints of the range (see the range defined in para 0083), and R and R′ are independently C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl; or

the formula:

wherein w, x, y, and z are additively a number between 0 to about 86, including the endpoints of the range (see the range defined in para 0083), and R and R′ are independently C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl; or

the formula:

wherein w, x, y, and z are additively a number between 0 to about 86, including the endpoints of the range (see the range defined in para 0083), and R, R′ and R″ are independently C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl.

In another embodiment a quenching composition containing one such non-polymeric amidoamine can be present in a hydroxyl-containing diluent comprising water, in which the mole ratio of the primary polyamine to monobasic acid provides at least one free amino group, and water is added at the end of the condensation reaction. In another embodiment, the composition containing the non-polymeric amidoamine has all of its amino groups converted to amide. In this case, the condensation products retain defoaming and lubricant properties, but do not act as antagonists to microorganisms. In still another embodiment, the diluent lacks water and the mole ratio of the primary amine to monobasic acid provides at least one free amino group.

Other Components for Quenching Compositions

Still other embodiments of the quenching compositions containing an polyamidopolyamine or non-polymeric amidoamine described herein also contain other components. Thus other additional components of the final use compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines described herein include one or any combination of additional agents, including but not limited to, coalescing/drying agent, rheology modifier, ester, carboxylic acid, fatty acid, emulsifier, amine, thickener, lubricant, dispersant, antioxidant, alkaline compound, builder, solvent, amphipathic agent, carrier, preservative, buffer, metal deactivator, dye, fragrance, caustic agent, wetting agent, sequestering agent, fungicide, defoamer, antioxidant, die release fluid, antiwear agent, viscosity modifier, de-emulsifier, natural triglyceride, animal fat, vegetable oil, fatty acid ester, and/or a phosphate ester. Still other optional components may be included in the concentrate and/or composition and may be selected by those skilled in the art. These additional components include, but are not limited to, salts, buffers, pH adjustors, enzymes, surfactants, tackifying agents, scale inhibitors, catalysts, clay control agents, friction reducers, corrosion inhibitors, dispersants, flocculants, H2S scavengers, CO2 scavengers, oxygen scavengers, lubricants, gelling agent, crosslinking agent, wetting agents, relative permeability modifiers, resins, adhesives, and coating enhancement agents.

In one embodiment, such other components include other known quenching polymers used in conjunction with the polyamidopolyamine and/or non-polymeric amidoamine compound as an additional quenching component.

Suitable polymers useful in the aqueous quenchants and methods described herein are known in the art. Suitable polymers include polyvinyl alcohol; polyalkylene glycol (PAG); sodium polyacrylate (ACR); polyvinyl pyrrolidone (PVP); polyethyloxazoline (PEOX); and hybrid polymer quenchants. See, e.g., Eshraghi-Kakhki et al, International Journal of ISSI, 6(1):34-8 (2009). Other suitable polymers include, for example, those described in U.S. Pat. No. 3,220,893, which discusses a quenching medium containing an oxyalkylene polymer having oxyethylene and higher oxyalkylene groups which form a desirable covering over the metal substrate surface during quenching. The polymer layer that coats the metal permits relatively short quenching times, thereby resulting in minimum internal stress of the metal substrate, minimum distortion of the metal substrate, and imparts uniform hardenability of the metal substrate. Another suitable aqueous quenching media is described in US Patent Publication No. 2009/0095384 which contains a polyvinylpyrrolidone/polyvinylcaprolactam copolymer; and a non-ionic, water-soluble or water-dispersible polymer including one or more of (a) a substituted oxazoline polymer; (b) a poly(oxyethyleneoxyalkylene) glycol polymer; or (c) a polyvinylpyrrolidone polymer.

Further, U.S. Pat. Nos. 3,902,929, 4,826,545, and RE 34119 discuss aqueous quenching media containing a polyvinylpyrrolidone and U.S. Pat. No. 4,087,290 discusses an aqueous quenching medium containing a water-soluble polyacrylate, such as a sodium polyacrylate, which forms a vapor blanket about the metal substrate during the quenching operation.

Suitable quenchants are known under various proprietary names, including, without limitation, AQUA-QUENCH® 140 (Houghton Int'l); AQUA-QUENCH® 145 (Houghton Int'l); AQUA-QUENCH® 245 (Houghton Int'l); AQUA-QUENCH® 251 (Houghton Int'l); AQUA-QUENCH® 260 (Houghton Int'l); AQUA-QUENCH® 3699 (Houghton Int'l); AQUA-QUENCH® C (Houghton Int'l); PARQUENCH®60 and PARQUENCH®90; POLYQUENCH® 10, POLYQUENCH® 15, and POLYQUENCH® 20; PLASTIQUENCH™; and SPEED QUENCH™ 1 (all Park Metallurgical Corporation); AQUATENSID® (Petrofer); and the UCON™ (DOW Chemical Company) series of quenchants. Other suitable quenchants are known in the art.

In certain embodiments, the aqueous quenching fluid comprises capped polyalkylene glycols, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone copolymers, polyethyloxazoline (PEOX), polyethyloxazoline copolymers, polyacrylate, polyacrylate copolymers, or mixtures thereof. In certain other embodiments, the aqueous quenching fluid comprises uncapped polyalkylene glycols, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone copolymers, polyethyloxazoline (PEOX), polyethyloxazoline copolymers, polyacrylate, polyacrylate copolymers, or mixtures thereof In still other embodiments, the aqueous quenching fluid comprises capped and uncapped polymers, such as combinations of those identified herein. In one embodiment, the aqueous quenching fluid (bath and/or spray) comprises polyalkylene glycol (e.g., Houghton Aqua Quench® 365). In another embodiment, the aqueous quenching fluid (bath and/or spray) comprises a polyvinylpyrrolidone (PVP) polymer (e.g., Houghton Aqua Quench® C). In another embodiment, the aqueous quenching fluid (bath and/or spray) comprises a PEOX polymer (e.g., Houghton Aqua Quench® 3600). In still another embodiment, the aqueous quenching fluid (bath and/or spray) comprises PVP/PVC, vinylpyrrolidone/vinyl caprolactam copolymer (e.g., Houghton Aqua Quench® 4000).

In still another embodiment, the quenching fluid (bath and/or spray) one or more additional components include a carrier. In one example, the carrier is water. The carrier may be included in the quenching medium, thereby permitting use of the product by the customer without addition of further carrier. Alternatively, the carrier is present in the quenching medium in sufficient amounts to provide a stable solution for further dilution by the customer prior to use. The carrier may also be added by the customer to a concentrated quenching medium composition prior to use. However, more water made be added to the composition to ensure that the final quenching medium contains sufficient water for use by the customer.

Addition components with antimicrobial activity in addition to that activity provides by the polymeric polyamidopolyamines or non-polymeric amideamines may optionally be added to the quenching baths or sprays used in the processes described herein to prevent or reduce the accumulation of microorganisms in the system. The particular antimicrobial selected will depend on the process parameters, including aqueous quenching fluid, hydraulic fluid, the metal or metal alloy, the dimensions of the metal or metal substrate being quenched, among others. Such components include, for example biocides, bactericides or fungicides, e.g. polyaminopropylbiguanide (obtainable from Arch under the trade name CosmocilCQ™), paraformaldehyde, glutaraldehyde, phenoxyethanol, 2,4-dichlorobenzyl alcohol, 2,3-dibromo-3-nitrilopropionamide, and 5-chloro-2-methyl-2H-isothiozol-3-one. Suitable biocides are known in the art, including, without limitation, CONTRAM™ biocides (Lubrizol); the BIOBAN™, DOWICIDE™, KATHON™, ROCIMA™ and KORDEK™ brand biocides (Dow Chemical); MERGAL® brand biocides (ECT CV Corp.); TROYSHIELD® (Troy Technical Corp) (iodopropynyl butylcarbamate). One of skill in the art would be able to make such a selection, taking into consideration the teachings of this specification. In one embodiment, the antimicrobial is the Grotan® reagent (Troy Corporation). In another embodiment, the antimicrobial may be selected from the list of microbicides discussed in the catalog “Metalworking”, Buckman Laboratories, Inc., 2010, which is herein incorporated by reference in its entirety. In a further embodiment, the antimicrobial is the Busan® 1060 reagent (Buckman Laboratories). Other examples of suitable antimicrobials are the KATHON™ 886 MW product and KATHON™ 893 MW product (Dow Chemical Company). Other suitable biocides may be readily determined by one of skill in the art.

Still additional components include preservative, and also further compounds such as ethanolamine, polyalkylene oxides, polyethylene glycols. ethanol amine or amine soaps, buffer, metal deactivator, dye, fragrance, caustic agent, wetting agent, sequestering agent, among others.

Conventional antifoams/defoamers include components such as silicone oils, fatty alcohol alkoxylates, alcohol alkoxylates, carboxylic esters or phosphoric esters. Suitable antifoam agents are known in the art, including, without limitation, the TEGO® brand antifoams (Evonik Industries); XIAMETER® brand antifoams (Dow Coming); SAF-115, SAF-125, SAF-150, SAF-151, SAF-250, SAF-251 (Silchem Inc.); SURTECH® antifoams (PMC Crystal); Additive 2901 (Quaker Chem); and TROYKYD® brand defoamers (Troy Technical Corp). Other suitable antifoams can be readily determined by one of skill in the art.

“Antioxidants” as described herein are useful additives for preventing the degradation of the hydraulic fluid or quenching bath or quenching spray through oxidation. Such antioxidants may be selected from among an aromatic amine, quinoline, and phenolic compounds. In one embodiment, the antioxidant is an alkylated diphenyl amine (Vanlube® NA reagent, polymerized trimethyl-dihydro-quinoline (Vanlube® RD reagent) or 4,4′-methylene bis(2,6-di-tert-butylphenol).

“Corrosion inhibitors” may be selected from the battery of conventional corrosion inhibitors for both ferrous and non-ferrous metals used in the industry. In one embodiment, the corrosion inhibitor is tolyltriazole. Another corrosion inhibitor is sodium nitrite, borax, amines, ammonium salts of organic acids, phosphoric esters, alcohol alkoxylates, or 2-butyne-1,4-diol. However, other known and commercially available corrosion inhibitors could readily be used by one of skill in the art, taking into consideration the teachings of this specification.

“De-emulsifiers” as described herein may also optionally be included in the quenching baths or quenching sprays utilized herein. This is particularly useful when high agitation rates are utilized during the process. However, their inclusion is not required. One of skill in the art would be able to select a suitable de-emulsifier for use herein, taking into consideration the teachings of this specification.

These “additional” components may be present in the composition at about 0.05% to up to about 20% by weight. In one example, these components are present in combination in the quenching compositions at about 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20% by weight, or fractional percentages therebetween.

In one exemplary embodiment, a metal quenching media therefore advantageously comprises 60 to 99.8% by weight of water as carrier, 0.5 to 40% polyamidopolyamine or non-polymeric amidoamine, and 0.1 to 20% by weight of customary additives. In still another example, an aqueous quenching medium contains a polyamidopolyamine having a weight average molecular weight of about 10,000 in a concentration of about 25% to about 35% by weight and 55% water. The aqueous quenching medium may also contain about 0.05% to about 10% by weight of additives, including, without limitation, corrosion inhibitors and defoamers.

The invention also provides a concentrate which contains the polyamidopolyamine and/or non-polymeric amidoamine components described above. This concentrate may be utilized by those skilled in the art for preparing an aqueous quenching medium useful in the heat treatment of metal substrates. In one example, the concentrate contains water and at least about 0.5% by weight of a polyamidopolyamine and/or non-polymeric amidoamine described above. In another example, the concentrate contains water and about 0.5% to 40% by weight of these polyamidopolyamine and/or non-polymeric amidoamines. In a further example, the concentrate contains about 5% to about 20% of these polyamidopolyamine and/or non-polymeric amidoamines described above.

In still other embodiments, the composition comprising the polyamidopolyamines and/or non-polymeric amidoamines will be combined with additional components, which are those necessary to employ the composition in a final “use” composition. In one embodiment, the composition may provide needed and multiple properties to a metal cutting fluid. In another embodiment, the composition may provide its multiple properties to a heat treating fluid or hydraulic fluid. In a further embodiment, the composition comprising the polyamidopolyamines can be used in a metal working fluid for the purposes of application to metals for metal rolling, metal cleaning, metal cutting, metal drawing, or metal forming. In this embodiment, the compositions described herein are useful as lubricants and bioresistance and defoaming components. In a further embodiment, the composition comprising the polyamidopolyamines can be used in a hydraulic fluid. In still other embodiments, the additional components are those necessary to employ the composition in a cleaning fluid, desirably for high pressure applications which require non-foaming components. In another embodiment, the compositions may be useful as additives to rust preventatives. Further embodiments for use of the compositions include as anti-microbials in oil pipelines or offshore use (e.g., blow-out preventatives). The compositions are also useful in forming uses, as a film-forming lubricant, or as additives or compositions used in wire drawing, aluminum rolling, and ferrous rolling.

Still other embodiments for use of some of these compositions are as anti-microbials to prevent the formation of biofilms on various surfaces. Other embodiments include use as additives to coating fluids. In still another use, the compositions can be used in Yankee dryer coatings in the manufacture of tissue and toweling. In still other embodiment, the additional components are those necessary to employ the composition in a pigment-based fluid, e.g., paints. In still other embodiment, the additional components are those necessary to employ the composition as a lubricant. In still other embodiment, the additional components are those necessary to employ the composition in protective fluids for application to porous and non-porous surfaces, e.g., e.g., metal, plastic, polyurethane, and on fibrous substrates, e.g., paper, wood, cardboard, wallpaper, insulation, carpeting, ceiling tiles, textiles, wallboard and fabric, such as cotton, to discourage microbial degradation of biofilm thereon. As one example, the compositions may be useful in coatings that prevent microbially induced corrosion in sprinkler pipes or other metal piping.

In another embodiment of compositions and uses, the advantage of the polyamidopolyamine-containing composition is that it has creping properties that are useful in adhesives (see e.g., U.S. Pat. No. 5,633,309 and 5,602,209). In another embodiment, the compositions are useful to provide mold-resistance to cellulose surfaces, such as paper, wood, wall board, ceiling tiles, and to wood preservatives. The compositions also provide microbial resistance to cotton fibers. Still further uses include formulations with chitosan, a natural polymer, to protect surfaces and fibers. As one example, nylon or similar type fibers may be prepared with these compositions to provide built-in microbial resistance. Still other uses of these compositions and compounds may be determined by one of skill in the art considering the teachings of this specification.

Thus other additional components of the final use compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines described herein include one or any combination of additional agents, including but not limited to, coalescing/drying agent, rheology modifier, ester, carboxylic acid, fatty acid, emulsifier, amine, thickener, lubricant, dispersant, antioxidant, alkaline compound, builder, solvent, amphipathic agent, carrier, preservative, buffer, metal deactivator, dye, fragrance, caustic agent, wetting agent, sequestering agent, fungicide, defoamer, antioxidant, die release fluid, antiwear agent, viscosity modifier, de-emulsifier, natural triglyceride, animal fat, vegetable oil, fatty acid ester, and/or a phosphate ester. Still other optional components may be included in the concentrate and/or composition and may be selected by those skilled in the art. These additional components include, but are not limited to, salts, buffers, pH adjustors, enzymes, surfactants, tackifying agents, scale inhibitors, catalysts, clay control agents, friction reducers, corrosion inhibitors, dispersants, flocculants, H₂S scavengers, CO₂ scavengers, oxygen scavengers, lubricants, gelling agent, crosslinking agent, wetting agents, relative permeability modifiers, resins, adhesives, and coating enhancement agents.

Still other additional components for admixture with the compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines described herein are additional biocides or antimicrobials, e.g., the biocides described in U.S. Pat. Nos. 5,332,430 and 8,276,663, which are incorporated by reference herein. The compositions described herein with the hydroxyl-containing diluent generally contains about 1% to about 10% w/w of an antimicrobial composition, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% w/w or numbers therebetween of the antimicrobial polyamidopolyamine or the same weight percent in combination with another known antimicrobial. In one embodiment, the antimicrobial composition contains about 3 to about 7% w/w total antimicrobial compound (i.e., the polyamidopolyamine only or with an additional biocide).

In still other embodiments, the compositions containing the polyamidopolyamines and/or non-polymeric amidoamines also contain a natural biopolymer. In one embodiment, the natural biopolymer is a high molecular weight polyamide. In another embodiment, the natural biopolymer is a chitosan. As one example the composition may be used to protect a polyurethane surface when the composition contains the polyamidopolyamine described herein and chitosan. Such a composition may be applied directly to the surface and allowed to dry. Furthermore, the polyamidopolyamines and non-polymeric amidoamines (reactions with monobasic acids) can be neutralized with fugitive acids, such as acetic acid. Compositions containing these reaction products can be applied in water and remain as a coating when the acetic acid and water evaporate.

Still other compositions employing the polyamidopolyamine and/or non-polymeric amidoamines compounds and compositions described herein may be prepared by one of skill in the art applying the teachings of this specification.

Methods of Use of These Compositions

Various methods of heat treating metal substrates are known and include heating a metal substrate to an elevated temperature and then cooling. The cooling step, which is known in the art as “quenching”, typically is performed rapidly and is accomplished by either immersion quenching or spray quenching. Immersion quenching involves immersing the hot metal substrate in a liquid quenching medium, i.e. a quenching bath. Spray quenching involves spraying quenchant on the heated metal part as it travels through a quench barrel or quench ring. The process of quenching involves the use of certain hydraulic equipment, which requires hydraulic fluids for performance. These quenching systems typically use large amounts of both aqueous quenchant and hydraulic fluid. The amount of quenchant used can be sizable depending upon the size of the metal product that is being quenched.

Thus the polyamidopolyamine and non-polymeric amidoamines compositions described herein can also be used in compatible fluids, e.g. hydraulic fluids. Such compatibility is important in circumstances in which these fluids contaminate each other during use.

In one embodiment, a process for increasing the efficiency of a metal quenching bath comprises the following steps, including providing in a container or quenching tank a metal quenching bath comprising a polyamidopolyamine and/or non-polymeric amidoamine as described herein. Generally, metal or metal substrates enter the quenching bath at temperatures as high as 1600° C. While the bath is being used for quenching, the bath temperature is kept about 100° F. and 120° F. (i.e., 37.7° C. and 48.9° C.) to keep the quenching fluid at its desired quenching temperature.

In one embodiment, a process for increasing the efficiency of a metal spray quenching, comprises the following steps, including spraying a metal substrate with a quenching fluid containing a polyamidopolyamine and/or non-polymeric amidoamine as described herein. Generally, metal or metal substrates enter the quenching ring or quench barrel at temperatures as high as 1600° C. While the spray is being used for quenching, the spray temperature is kept between about 100° F. and 120° F. (i.e., 37.7° C. and 48.9° C.) to keep the quenching fluid at its desired quenching temperature.

The processes of the present invention are performed using conventional metal quenching bath equipment or quenching spray equipment. One of skill in the art would readily be able to select suitable quenching equipment for use in quenching the selected metal, taking into consideration the teachings of this specification.

When used in a quenching composition, it is anticipated that the compositions comprising the polyamidopolyamines will be used at a concentration of between about 10 to about 30% by weight of the resulting use composition, and can replace or work in tandem with another quenchant, while also replacing one or more typical quenching additives for lubricity, bio resistance and/or foam control. Compositions containing non-polymeric amidoamines are anticipated to work with the polyamidopolyamines in this context, or as additives to other known quenchant formulations. See, for example, U.S. Pat. Nos. 8,764,914; 4,486,246; 4,528,044; 4,381,205; and 4,404,044 which describe some examples of known quenching fluids.

In another aspect, a method of altering surface behavior of a liquid is provided. Foam, pockets of air that are entrapped in a liquid, is often present in coolants and processing liquids and causes problems. Foam can negatively influence the cooling efficiency or lubrication properties of the metalworking fluid and limits the visual inspection of the working process. Further problems include reduction of pump efficiency; reduced capacity of pumps and storage tanks; bacterial growth; dirt flotation/deposit formation; reduced effectiveness of the fluid; and downtime to clean tanks. In one embodiment, the liquid is an aqueous quenching medium. In one embodiment, the method includes adding to the liquid the polyamidopolyamine and/or non-polymeric amidoamine compound described above. The present invention includes the use of the polyamidopolyamine and/or non-polymeric amidoamine for altering surface behavior, e.g., for use as an anti-foam, defoam or low-foaming agent and/or a deaeration agent. In one embodiment, polyamidopolyamine and/or non-polymeric amidoamine is added to an aqueous quenching medium as an anti-foam agent. The polyamidopolyamine and/or non-polymeric amidoamine compound described herein can be used alone as an antifoam or low foam component in the compositions or in conjunction with another antifoam agent.

In another aspect, a method of providing antimicrobial or bioresistant properties to a metalworking fluid is provided. In one embodiment, the method includes adding a described polyamidopolyamine to the metalworking fluid. In another embodiment, the method includes adding a non-polymeric amidoamine to the metalworking fluid. In another embodiment, a mixture of these compounds can be added for enhance bioresistance in a quenching fluid. In one embodiment, the metalworking fluid is an aqueous quenchant. If left untreated, dangerous microorganisms are inevitable in aqueous metalworking fluids due to the water content, elevated temperatures, and contaminants. Good maintenance of metalworking fluid re-circulation systems can extend the lifetime of coolants and ensure the quality of the tools produced. In metalworking fluids, as in the other water-based environments, microorganisms usually live in the form of biofilms, the communities of bacteria and fungi attached to the surface of sumps, metal parts and also to each other. Biofilms exhibit very high resistance to biocides.

In one embodiment a described polyamidopolyamine can be used alone as an antimicrobial or bioresistant or in conjunction with one or more antimicrobial or bioresistant agents in a heat treating, e.g., quenching composition. In another embodiment, a described non-polymeric amidoamine can be used alone as a antimicrobial or bioresistant or in conjunction with one or more antimicrobial or bioresistant agents in these compositions. Non-polymeric amidoamine and polyamidopolyamine can be used together or in conjunction with one or more antimicrobial or bioresistant agents. In addition, polyamidopolyamine and/or non-polymeric amidoamine may also be used in conjunction with other anti-microbial techniques, such as the use of uv light or ozonation.

When employed as an additive to other known heat treating compositions, e.g., quenchants, it is anticipated that the present polyamidopolyamine and/or non-polymeric amidoamine -containing compositions will replace multiple components currently in use. In one embodiment, a composition described herein can be used simultaneously for its characteristics as both a lubricant and a defoamer, thereby replacing two components with a single component. Similarly, a composition described herein which has bioresistance or antimicrobial characteristics, as well as defoaming and/or lubricity characteristics may replace three other components in a suitable composition.

In general, when use as a defoamer, the polyamidopolyamines and/or non-polymeric amidoamines and/or compositions containing them can desirably replace silicone defoamers. It is anticipated that as a defoamer additive, the compositions or the compounds isolated therefrom may be use at a concentration of between about 0.1 to 0.5% by weight of the resulting use composition, e.g., metal working fluid. This range includes fractional numbers and the endpoints of the range, e.g., the present polyamidopolyamine and/or non-polymeric amidoamine—containing compositions can be added at e.g., 0.1, 0.2, 0.3, 0.4 and 0.5% by weight of the resulting use composition.

When used primarily as an additive for its anti-microbial/bioresistant characteristics, it is anticipated that the compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines will be used at a concentration of between about 1 to about 3% by weight of the resulting use composition, e.g., a paint or polyurethane coating fluid. This range includes fractional numbers and the endpoints of the range, e.g., the present polyamidopolyamine compositions can be added at e.g., 1.0, 1.3, 1.5, 1.7, 2.0, 2.2, 2.4, 2.6, 2.7, and 3.0% by weight of the resulting use composition. Most desirably, the compositions can be used as a formaldehyde-free anti-microbial.

When used primarily as an additive for its lubricant characteristics and optionally its bioresistant/antimicrobial characteristics, it is anticipated that the compositions comprising the polyamidopolyamines and/or non-polymeric amidoamines will be used at a concentration of between about 5 to about 30% by weight of the resulting use composition, e.g., a lubricating fluid that does not degrade in the presence of a microorganism. This range includes fractional numbers and the endpoints of the range, e.g., the present polyamidopolyamine compositions can be added at e.g., 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30% by weight of the resulting use composition.

Methods for quenching a metal comprise immersing or spraying a heated metal with any of the quenching compositions disclosed herein including any of the specific embodiments described in this specification. Use of the multi-functional polyamidopolyamine and/or non-polymeric amidoamines to replace multiple other components of a quenching fluid reduces the quenching costs for the customer, and produces less waste.

Embodiments

In addition to the embodiments described above, in the examples and in the claims, other embodiments described herein include the following:

In one embodiment, a composition comprises a polyamidopolyamine produced by the reaction of a polybasic acid and primary polyamine, which is linear, cyclic, branched or cross-linked, said polyamidopolyamine having a molecular weight of about 500 to about 100,000 and having one or more repeating pendant amino groups, wherein said polyamidopolyamine is of the Formula A wherein each polybasic acid is a dimer acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a and a′ are independently 1 or 2; b is 0, 1 or 2; and r is a number between 2 to about 10, including both endpoints of the range. In another embodiment, this composition is formed by the reaction having a 2:1 mole ratio of polyamine to dimer acid.

In another embodiment, the composition further comprises a polyamidopolyamine of the Formula A′, wherein a is 1, 2, 3, or 4, and said reaction has a 1:1 molar ratio of polyamine to dimer acid.

In another embodiment, the composition further comprises a polyamidopolyamine of the the Formula B, wherein each polybasic acid is a trimer acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a, c, d and e are independently 1 or 2; b is 0, 1 or 2; and r is a number between 3 to about 10, including both endpoints of the range.

In another embodiment, the composition further comprises a polyamidopolyamine of the Formula C, wherein each polybasic acid is a tetrabasic acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a, c, d, and e are independently 1 or 2; b is 0, 1 or 2; and r is a number between 4 to 10, including both endpoints of the range.

In still another embodiment, any one of these compositions described herein further comprises an organic hydroxyl containing diluent. In still another embodiment, any one of these compositions described herein further comprises water as a diluent. In still another embodiment, any one of these compositions described herein further comprises a water soluble acid to increase the solubility of the polyamidopolyamine and non-polymeric amidoamine in water.

In still another embodiment, any one of these compositions described herein is water-soluble or water dispersible. In still another embodiment, any one of these compositions described herein has a cloud point of about 25° C. to about 82° C., or of about 77° F. to about 180° F., in water. In still another embodiment, any one of these compositions described herein is characterized by one of more of the characteristics of low-foaming, non-foaming, or defoaming properties and/or antimicrobial or bioresistant properties and/or lubricating properties. In still another embodiment, any one of these compositions described herein has a pH of about 8 to about 11.

Use compositions containing any of the polyamidopolyamine composition and other optional components can be a metal working fluid, an aqueous quenchant fluid, a cleaning fluid, a hydraulic fluid, a protective coating fluid, a lubricant, a pigment-based fluid, or a protective coating for fibrous or metal surfaces. Other use compositions can comprise the above described compositions and an antimicrobial composition or a fungicide.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group involves condensing a polyamine comprising a primary amino group, and a C₃ to C₁₆ polybasic acid or derivative thereof, optionally in the presence of an organic hydroxyl-containing diluent.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group involves condensing a polyamine comprising three primary amino groups, and a C₃ to C₁₆ polybasic acid or derivative thereof, optionally in the presence of an organic hydroxyl-containing diluent.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group involves condensing a two polyamines comprising three amino groups and a C₃ to C₁₆ polybasic acid or derivative thereof.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group involves condensing a a polyamine comprising three amino groups and two C₃ to C₁₆ polybasic acids or derivative thereof.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine having a molecular weight of about 500 to about 100,000 and comprising a primary amino group involves condensing a a polyamine comprising three amino groups, a polyamine comprising two amino groups, and a C₃ to C₁₆ polybasic acid or derivative thereof.

In still another specific embodiment, a method for preparing a composition such as described herein that comprises a polyamidopolyamine (a) reacting a polybasic acid with a polyamine and an optional hydroxyl-containing solvent to produce a first polyamidopolyamine as a reaction product; (b) reacting the product (a) with the same or different a polybasic acid and an optional hydroxyl-containing solvent to produce another polyamidopolyamine as a subsequent reaction product; (c) performing additional sequential condensation reactions by reacting the polyamidopolyamine reaction product of each preceding condensation reaction with the same or different polybasic acid and an optional hydroxyl-containing solvent, and (d) terminating the reaction sequence when the composition demonstrates a desired characteristic selected from anti-foaming, defoaming, lubricity, bioresistance, antimicrobial activity or any combination thereof. The resulting composition comprises a polyamidopolyamine, which is a linear, cyclic, branched or cross-linked amide comprising multiple primary amine groups.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include a step for further terminating additional free amino groups to amide acids or salts with cyclic anhydride to cap amino groups at a temperature below the condensation reaction temperature.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include adding an organic hydroxyl-containing diluent or solvent at the initiation of the reaction.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include adding water or an organic hydroxyl-containing diluent or solvent at the end of the reaction to adjust viscosity of the composition.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include the use of a polybasic acid comprising two C(O)OH.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include use of the same polyamines or different polyamines in each condensation step.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include having a mole ratio of polybasic acid to polyamine that is equal to or greater than about 1: (1×), wherein X is the number of C(O)OH groups in the polybasic acid.

In still another specific embodiment, these various methods for generating the compositions described herein optionally include having a mole ratio of the polybasic acid to the polyamine is about is about 1:1, with an optional organic hydroxyl-containing solvent.

In still another specific embodiment, these various methods for generating the compositions described herein use as the polyamine triaminononane or 4-aminomethyl-1,8-octanediamine.

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein R¹, R³ and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R⁴ and R⁶ are independently methyl, ethyl, propyl, or butyl; and a, b and c are additively a number between 0 to about 90, including both endpoints of the range):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein s, t and u are additively a number between 3 to about 90, including both endpoints of the range):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein R¹ is H, methyl, ethyl, propyl or butyl; R², R³, and R⁴ are, independently, methyl, ethyl, propyl, or butyl; and e and f are additively a number between 0 to about 90, including both endpoints):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula

NH₂CH(CH₃)CH₂—(O—CH₂CH₂)_(g)—(O—CH₂CH(CH₃))_(h)—(O—CH₂CH(CH₃))—NH₂

wherein g and h are additively a number between 0 to about 90, including both endpoints of the range.

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein R¹, R³, R⁵ and R⁷ are independently H, methyl, ethyl, propyl or butyl; R², R⁴, R⁶ and R⁸ are independently is methyl, ethyl, propyl, or butyl; and w, j, k and m are additively a number between 0 to about 90, including both endpoints of the range):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein h, n, o and p are additively a number between 4 to about 90, including both endpoints of the range):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula (wherein R¹, R³, and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R⁴, and R⁶ are independently methyl, ethyl, propyl, or butyl; and a′, b′ and c′ are additively a number between 0 to 90, including both endpoints of the range):

In still another specific embodiment, these various methods for generating the compositions described herein use a polyamine of the formula ((wherein e′, f′ and g′ are additively a number between 3 to 90 including both endpoints):

In still another specific embodiment, a composition as described herein comprises a non-polymeric amidoamine, which is a linear or branched amide containing a primary amine group, said non-polymeric amidoamine having a molecular weight of about 290 to about 5000. In one embodiment, such a composition is produced by the reaction of a monobasic acid and a primary amine. In one embodiment, one such composition further comprises an amide comprising a diamide, a triamide or a tetraamide, or a mixture thereof.

In another embodiment, one such composition further comprises a non-polymeric amidoamine, which is a linear or branched amide containing a primary amine group, said non-polymeric amidoamine having a molecular weight of about 290 to about 5000.

Another specific embodiment of various compositions described herein contain a non-polymeric amidoamine of Formula F, wherein x, y, and z are, are additively a number between 3 to about 90, including both endpoints of the range; and R¹ is C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl.

Another specific embodiment of various compositions described herein contain a non-polymeric amidoamine of Formula G, wherein x, y, and z are, additively a number between 3 to about 90, including both endpoints of the range; and R¹ and R² are, independently, C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl.

Another specific embodiment of various compositions described herein are those compositions produced by a condensation reaction wherein the reactants comprise an acid and a polyamine, wherein the acid is a polybasic acid, a monobasic acid, or both a polybasic acid and a monobasic acid, in the optional presence of an organic hydroxyl-containing diluent.

The following examples are illustrative only and are not intended to limit the present invention.

EXAMPLE 1 Antimicrobial Activity of Polyamidopolyamine Composition 3533-171

The results of this experiment are shown in FIG. 1.

A polyamidopolyamine composition of Formula A, referred to as 3533-171, was produced by a condensation reaction of 2 moles of the Jeffamine® T403 polyetheramine (Huntsman Corporation) polyamine and 1 mole of adipic acid. The T403 amine is a trifunctional primary amine having an average molecular weight of approximately 440 with its amine groups located on secondary carbon atoms at the ends of aliphatic polyether chains.

The reaction was conducted at 160-165° C., with water as a diluent added at the end of the reaction. The final composition contained greater than about 73% of the polyamidopolyamine, up to 15% by weight of free T-403 polyamine and about 12.8% water. The composition has a cloud point (inverse solubility) at about 31° C. (88° F.).

The composition was diluted to 0.75% in water and was measured for the time in seconds that foam collapses to zero foam. The decay was less than 15 seconds. The polyamidopolyamine-containing composition 3533-171 was evaluated for anti-microbial ability in the following assay. The pH for the composition was adjusted to approximately 9.3. The composition 0.75% by weight diluted polyamidopolyamine composition 3533-171 contained 0.54% by weight polyamidopolyamine and 0.011% by weight T403 polyamine. This composition was added to deionized water that initially contained about 6 million Colony Forming Units (CFU)/ml of a mixed culture of bacterial species originally cultured from metal-working fluids. Bacterial growth measured was assessed over time of exposure to the compositions from 0 to 120 minutes, generating the graph of FIG. 1.

The graphical results indicate that the polyamidopolyamine-containing composition (3533-171) has a fast bacterial growth inhibition rate, i.e., marked anti-microbial activity.

EXAMPLE 2 Antimicrobial Activity of Polyamidopolyamine Composition 3587-17

The results of this experiment are shown in FIG. 2.

A polyamidopolyamine composition of Formula A, referred to as 3587-17, was produced by a condensation reaction of 2 moles of T403 polyamine (Huntsman) with 1 mole of azelaic acid, with triethanolamine (TEA) as a solvent. The reaction was conducted at 160-165° C. The final composition contained about 46% by weight of the polyamidopolyamine, up to 9.4% by weight of free T-403 polyamine and about 45% by weight triethanolamine. The composition has a cloud point (inverse solubility) at about 24° C. (75° F.).

The composition 3587-17, diluted to 0.75% in water was measured for the time in seconds that foam collapses to zero foam. The decay was less than 15 seconds.

The polyamidopolyamine-containing composition 3587-17 was evaluated for anti-microbial ability in the following assay. The pH for the composition was adjusted to approximately 9.3. The composition 3587-17 at 0.75% by weight polyamidopolyamine contains 0.34% by weight polyamidopolyamine, 0.07% by weight free T403 polyamine, and 0.34% by weight TEA.

This composition was added to deionized water that initially contained about 4.5 million CFU/ml of a mixed culture of bacterial species originally cultured from metal-working fluids. Bacterial growth was assessed over time of exposure to the compositions from 0 to 120 minutes, generating the graph of FIG. 2.

The graphical results of FIG. 2 indicate that the polyamidopolyamine-containing composition 3587-17 shows marked anti-microbial activity.

EXAMPLE 3 Antimicrobial Activity of Polyamidopolyamine Composition 3581-5

The results of this experiment are shown in FIG. 3.

A polyamidopolyamine-containing composition of Formula A, referred to as 3581-5, was produced by a condensation reaction of 2 moles of T403 polyamine (Huntsman) with 1 mole of adipic acid, with TEA as a solvent. The reaction was conducted at 160-165° C. The final composition contained about 44.6% by weight of the polyamidopolyamine, up to 9.1% by weight of free T-403 polyamine and about 46.3% by weight TEA. The composition has a cloud point (inverse solubility) at about 50° C. (122° F.).

The composition 3581-5, diluted to 0.75% by weight in water, was measured for the time in seconds that foam collapses to zero foam, which was 60 sec.

The polyamidopolyamine-containing composition 3581-5 was evaluated for anti-microbial ability in the following assay. The pH for the compositions was adjusted to approximately 9.3. The 3581-5 polyamidopolyamine-containing composition at 0.75% by weight contained 0.334% by weight of the polyamidopolyamine, 0.07% by weight free T403 polyamine, and 0.35% by weight TEA).

This composition was added to deionized water that initially contained about 1.8 million CFU/ml of a mixed culture of bacterial species originally cultured from metal-working fluids. Bacterial growth was assessed over time of exposure to the composition from 0 to 120 minutes, generating the graph of FIG. 3.

The graphical results of FIG. 3 indicate that the polyamidopolyamine-containing composition (3581-5) shows marked anti-microbial activity.

EXAMPLE 4 Lubrication Activity

The results of this experiment are shown in FIG. 4.

The three polyamidopolyamine-containing compositions described in Examples 1-3 above were compared for lubrication ability with a commercial synthetic lubricant HOCUT® 767 (Houghton International Inc.) commonly used as a metal removal fluid. The HOCUT® 767 fluid was used as a 5% dilution in water, which equals about 0.75% active ingredients. All dilutions indicated are in deionized water.

The data was reported using the Falex Extreme Pressure test, as follows: This test uses a Falex pin and vee block machine to test the extreme pressure properties of lubricants. The pin is Falex #8 (AISI 3135 steel, rb 87-91, 10 rms maximum) and the vee blocks are the standard 1137 steel, Rc 2-24, 10 rms maximum, 96° block angle. The vee blocks are fitted into arms that can be closed by a ratchet wheel, putting increasing load on the pin that is rotating at 290 rpm. Gauges allow measurement of load, torque, and temperature. Once assembled, 70 ml of sample is poured into the cup, which immerses the test pieces. After a break-in for one minute at 250 pounds load, the load is increase 250 pounds at t time and held at that load for 30 seconds. Maximum Load for this test is 4500 pounds. Failure can occur by either of two modes: seizure between pin and blocks causing breakage of either the brass shear pin or steel pin; or wear is so high that at least 250 pounds of load are lost in 30 seconds or less.

FIG. 4 and Table 1 show the lubrication data reported as torque vs. load in pounds. Hocut 767 lubricant is used at 5% by weight dilution. Polyamidopolyamine-containing composition 3533-171 is used at 0.75% by weight dilution. Composition 3587-17 is used at 1.38% by weight dilution. Composition 3581-5 is used at 0.75% by weight dilution. All dilutions are in ionized water. The lower the torque and higher the load, the better the composition operates as a lubricant. As shown in these preliminary evaluations of FIG. 4, all of the polyamidopolyamine-containing compositions were comparable in lubrication with the synthetic fluid.

TABLE 1 LUBRICATION DATA Load/lbs. Torque applied to pin/ Composition Composition Composition HOCUT Using Falex 3533-171 3587-17 3581-5 767 Fluid 250 28 15 25 25 500 36 23 32 28 750 40 30 35 30 1000 43 30 37 32 1250 45 35 47 34 1500 46 37 47 38 1750 48 38 52 40 2000 57 46 55 45 2250 60 51 60 48 2500 60 61 50 2750 60 61 55 3000 67 60 68 3250 69 62 80 3500 68 70 84 3750 69 67 90 4000 65 65 4250 70 4500 71

EXAMPLE 5 Defoaming, Low Foaming and Deaeration Characteristics of Polyamidopolyamines

The product referred to as Houghto-Clean 3181 is a high foaming cleaner used in spray wash applications. Houghto-Clean 8131 spray cleaner was modified by replacing a chlorine capped defoaming surfactant (4%) with the polyamidopolyamine 3533-171. A second formulation was prepared using the polyamidopolyamine 3587-17. The results using a (a) Waring Blender Test and (b) a High Pressure Foam Test Simulator are provided.

A polyamidopolyamine composition referred to as 3533-171, was produced by a condensation reaction of 2 moles of the Jeffamine® T403 polyetheramine (Huntsman Corporation) polyamine and 1 mole of adipic acid. Water (12.8%) was added at the end of the reaction to reduce viscosity.

3587-17 is the condensation reaction of 2 moles of the Jeffamine® T403 polyetheramine (Huntsman Corporation) polyamine and 1 mole of azelaic acid. The reaction was run in 45% triethanolamine (TEA) that was not removed.

Waring Blender Shear Test

The Waring blender test was conducted at 3% v/v dilution. 200 mL of solution was placed in the blender. The blender was operated for 30 seconds. Solution was poured into 500 mL graduated cylinders. Foam volume and break time were noted.

Foam Test Results are displayed in Table 2.

Houghto- Houghto- Houghto- Clean ™ 8131 Clean ™ 8131 Clean ™ 8131 original with 3533-171 with 3587-17 Foam Vol (mL) 175 0 0 Foam Break Time >5 minutes NA NA

No foam was observed for the two modified formulas.

Houghto-Clean™ 8131 product modified with 3522-171 or 3587-17 foams significantly less than the original formula in a Waring blender foam test.

High Pressure Foam Tests

The purpose of these experiments is to determine if 3533-171 will reduce foaming. Dilutions of each fluid to be tested were prepared at 3% v/v using RO water. Following the procedure described below, the solutions were tested at low pressure, then at high pressure twice.

Temperature was monitored between foam tests. The high pressure foam test simulator procedure involves: Filling system by pouring 1500 mL of fluid into spray chamber. Fluid will flow through and collect in the graduated cylinder below the fill chamber. Then the pump is turned on and the pressure set to approximately 80 psi. The pump is run for 30 seconds, and then foam and foam break time are recorded. When the sample is clear and no foam remains, the pump is turned on and pressure set to approximately 500 psi. Pump is run for 30 seconds. Foam and foam break time are measured. Test is repeated as necessary.

The results show that the temperature of the solutions increased slightly throughout testing, with 3.4° being the change in temperature between initial and final foam test. This temperature change is not likely to affect foaming or foam break times.

In general, the foam height increased when a given solution was subjected to a higher pressure. Houghto-Clean™ 8131 product (original) foams more than the modified versions. However, cleaner samples modified with 3533-171or 3587-17 displayed less foam overall in comparison to the original Houghto-Clean™ 8131 sample. The sample of original Houghto-Clean™ 8131 product had the longest foam and entrained air break times. The cleaner modified with 3533-171 had the shortest foam and entrained air break times. For the sample modified with 3587-17, foam and entrained air break times were similar.

TABLE 3 Comparison data for high pressure foam tests. Houghto- Houghto- Houghto- Clean ™ Clean ™ Clean ™ Pressure Other Test 8131 8131 with 8131 with Conditions Conditions original 3533-171 3587-17 Low (80 Temp initial (° F.) 72.6 71.0 71.2 psi) Temp final (° F.) 73.3 71.5 71.7 Foam Ht initial (cm) 30.3 29.5 30   Foam Break (min) 12:00 6:00 7:00 Entrained Air Break  8:30 5:30 7:00 (min) High (500 Temp initial (° F.) 73.3 71.5 71.7 psi) Run 1 Temp final (° F.) 74.4 72.6 72.9 Foam Ht initial (cm) 36.5 32.3 33   Foam Break (min) 46:00 4:00 6:00 Entrained Air Break 18:30 2:00 6:00 (min) High (500 Temp initial (° F.) 74.4 72.6 72.9 psi) Run 2 Temp final (° F.) 74.5 73.9 74.6 Foam Ht initial (cm) 37   33.5 31.5 Foam Break (min) 45:00 4:00 8:00 Entrained Air Break 24:00 2:00 8:00 (min)

EXAMPLE 6 Polyamidopolyamine and Characteristics

Polyamidopolyamine 3587-203 is a condensation reaction product of Huntsman Jeffamine T-403 (5 moles) and adipic acid (4 moles). The polyamidopolyamine was evaluated by gel permeation chromatography analysis (GPC) and/or characterized as a diacid product by NMR and MALDI mass spectrometry.

Polyamidopolyamine 3587-185 is a condensation reaction product of Huntsman Jeffamine T-403 (5 moles) and adipic acid (4 moles). The reaction was run in dipropylene glycol solvent, 50% of the charge. The polyamidopolyamine was evaluated by gel permeation chromatography analysis (GPC) and/or characterized as a diacid product by NMR and MALDI mass spectrometry.

Polyamidopolyamine 3533-85 is a condensation reaction product of Huntsman Jeffamine T-403 (2 moles) and adipic acid (1 moles). The polyamidopolyamine was characterized as a diacid product by NMR and MALDI mass spectrometry.

The following Table 4 compares the characteristics of these polyamidopolyamines:

TABLE 4 Semi-quantitation distribution Mole % Mole % Mole % by MALDI-TOF 3587-203 3587-185¹ 3533-85 Unreacted T-403 43.9 64.6 51 Condensation Products One T-403 + one adipic 15.3 18.2 0 Two T403 + one adipic 18.4 13.8 29 Three T403 + two adipic 12.9 2.6 12 Four T403 + three adipic 9.5 0.8 5 Five T403 + four adipic detected Mole Ratio: T403/adipic 5:4 5:4 2:1 Avg MW measured by GPC 6,240 — 2,240 Avg MW measured by MALDI-TOF 858 577 1,220 ¹Reaction run in in dipropylene glycol

The GPC measurement according to Organization for Economic Cooperation and Development Test 118 (OECD 118) appears more accurate in determining molecular weight for these compositions. The MALDI-TOF is semi-quantitative for product distribution.

Approximate calculated weight % of polyamidopolyamine and unreacted Huntsman T403 from the condensation reactions: A MW of 440 daltons was used for Huntsman T403; GPC data was used to determine the average MW of the polyamidopolyamines. Weight % were calculated from the mole % determined from the same quantitative MALDI-TOF analysis. Results are as shown in Table 5.

TABLE 5 Condensation reaction product: 3587-203 3533-85 Mole ratio T403/adipic 5/4 2/1 Avg MW of polyamidopolyamine by GPC 6,240 2,240 Wt % unreacted T403 5.2 17 Wt % of polyamidopolyamine 94.8 83

The GPC measurement according to Organization for Economic Cooperation and Development Test 118 (OECD 118) appears more accurate in determining molecular weight for these compositions.

EXAMPLE 7 Bioresistant Characteristics

Procedure: The test was run separately for bacteria and fungus. The bacteria inoculum was a mixed culture grown on Houghton fluids. The fungus test was run with the species, Aspergillus niger. Samples were continuously stirred at room temperature for the duration of the test. All fluids were tested at 0.75% in DI water with pH adjusted to 9.3. Bacteria and fungi were counted as colony forming units/ml (CFU/ml).

Test Formulations:

30A (amide rxn): 0.75% by wt 3587-167 in water with pH adjusted to 9.3. 3587-167 is the condensation product using Huntsman T403 and glycolic acid at a 1:1 mole ratio. It has no cloud point.

30B (amide rxn): 0.75% 3587-173 in water, adjusted to pH 9.3. 3587-173 is the condensation product using Huntsman T403 and lactic acid at 1:1 mole ratio. It has a cloud point of 142° F. (61° C.), which helps in defoaming.

Results: The results presented are for comparative analysis only. Table 6 shows the results for bacteria. Tables 7 and 8 show the results for fungus. Different bacteria and fungus species may give different results. % FR means % fluid resistance.

TABLE 6 Bacteria Inoculation: CFU/ml CFU/ml % Fluid CFU/ml % FR CFU/ml % FR Time since Inoculation: 0 min 6 min Resistance 30 min 2 hr % FR Total Days: 0 0 0 0 30A 2 × 10⁶ 1.8 × 10⁶ 10.0 6.7 × 10⁵ 66.5 3.4 × 10⁵ 83.0 30B 2 × 10⁶ 1.3 × 10⁶ 35.0 3.9 × 10⁵ 80.5 0 100.0

TABLE 7 Fungus (part 1) Inoculation: CFU/ml CFU/ml % CFU/ml % FR Time since 0 min 2 hrs Fluid 4 hrs Inoculation: Resistance Total Days: 0 0 % FR 0 30A 2.1 × 10⁵ 1.5 × 10⁵ 28.6 1.6 × 10⁶ 23.8 30B 2.1 × 10⁵ 1.0 × 10⁵ 52.4 6.0 × 10⁴ 71.4

TABLE 8 Fungus (part 2) Inoculation: CFU/ml % CFU/ml % FR Time since 8 hrs Fluid 24 hrs Inoculation: Resistance Total Days: 0 % FR 1 30A 3.0 × 10⁴ 85.7 80 100.0 30B 3.0 × 10⁴ 85.7 40 100.0

EXAMPLE 8 Quenching Metal Substrates Using Aqueous Quenching Media

Experiments are conducted to determine cooling times using quenching compositions containing a polyamidopolyamine or non-polymeric amidoamine as described herein. The IVF Quenchotest (The Swedish Institute of Production Engineering Research) is utilized and includes the IVF data acquisition/recording unit, test probe, probe handle and furnace. The test probe (600 mm in length and 12.5 mm diameter of the Inconel® 600 probe enclosing a type K thermocouple —NiCr/NiAl— with a diameter of 1.5 mm) complies with the specification for testing quenchants as established by the International Federation for the Heat Treatment of Materials (IFHT). The furnace thermostat controls the power supplied to the furnace through diode rectification and is operated without a controlled atmosphere. The furnace temperature is adjusted to about 1625° F. (885° C.).

In each run, the metal substrate is heated to a temperature of about 1571° F. (855° C.) to about 1600° F. (870° C.) and then immersed in 1.0 kilograms of an aqueous quenching media containing a polyamidopolyamine described above which are maintained at a temperature of about 100° F. (40° C.). Data acquisition begins when the test probe temperature of the aqueous quenching medium reaches about 1562° F. (849° C.) and is acquired for about 60 seconds, i.e., until the temperature reached about 300° F.

After data collection, cooling curves are obtained using the data collected using the various polyamidopolyamine mixtures. Cooling times are determined from the cooling curves during which the test specimens are cooled from 1562° F. (849° C.) to less than 203° F. (95° C.).

Results are shown in FIGS. 5-9.

FIG. 5 is a cooling curve showing the comparison of polyamidopolyamine reaction products with water and Aqua Quench 260 (AQ260). AQ 260 is a commercial product supplied by Houghton International to slow down the quenching effect of water. Product 3587-193 is a polyamidopolyamine, the reaction of Huntsman Jeffamine T403 (10 moles) with adipic acid (9 moles). The reaction is performed in approximately 44% dipropylene glycol (DPG). The DPG remains in the reaction mixture. Cloud point (1%) approximately 81° Fahrenheit. The cooling curve measurements were made using the IVF quenchometer. Table 9 shows the parameters of the test leading to the curves of FIG. 5.

TABLE 9 13% 260 PROPERTY UNIT 1.IVF 3587-193.2.IVF WATER.IVF Max cooling rate C./s 177.43 187.03 207.67 Temp at Max C. 663.89 624.54 619.47 Cooling Rate Temp at Start of C. 844.3 815.88 844.21 Boiling Temp at Start of C. 156.28 137.64 57.68 Convection Cooling Rate at C./s 66.26 80.83 95.22 300 C. Time to 600° C. s 2.34 3.6 1.83 Time to 400° C. s 3.83 4.91 2.93 Time to 200° C. s 7.25 7.81 5.31 Theta 1 C. 844.36 815.19 843.97 Theta 2 C. 287.89 237.26 250.31 HP-IVF (oils) 2311.62 2565.11 3194.38 HP-IVF (polymers) 1339.89 1603.51 1874.86 OPERATION PARAMETERS Product Type Various Medium Temp 26 Medium concentration Various Agitation Rate (m/s) Moderate

FIG. 6 shows similar curves produced using product 3533-85-2 in the IVF method. 3533-85-2 is the product of a condensation reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1 mole). Cloud point (0.75%), approximately 86° F.; weight average molecular weight, 2,240; determined by gel permeation column chromatography (GPC). Table 10 shows the parameters of the test leading to the curves of FIG. 6.

TABLE 10 13% 260 3533-85 PROPERTY UNIT 1.IVF 2.IVF WATER.IVF Max cooling rate C./s 177.43 229.23 207.67 Temp at Max C. 663.89 585.34 619.47 Cooling Rate Temp at Start of C. 844.3 824.16 844.21 Boiling Temp at Start of C. 156.28 139.13 57.68 Convection Cooling Rate at C./s 66.26 92.74 95.22 300 C. Time to 600° C. s 2.34 3.03 1.83 Time to 400° C. s 3.83 4.06 2.93 Time to 200° C. s 7.25 6.51 5.31 Theta 1 C. 844.36 823.02 843.97 Theta 2 C. 287.89 226.32 250.31 HP-IVF (oils) 2311.62 3097.66 3194.38 HP-IVF (polymers) 1339.89 1868.75 1874.86 OPERATION PARAMETERS Product Type Various Medium Temp 26 Medium concentration Various Agitation Rate (m/s) Moderate

FIG. 7 shows the curves produced by the same method using product 3587-17-2 in the IVF method. 3587-17-2 is the product of a condensation reaction of Huntsman Jeffamine T 403 (2 moles) with azelaic acid. The reaction is run in 45% triethanolamine. The DPG and TEA are used as solvents for the reaction and also form the intermediate ester which is then converted to amido, releasing that solvent. The triethanolamme remains in the reaction mixture. Cloud point 0.75%, approximately 75° F. Table 11 shows the parameters of the test leading to the curves of FIG. 7.

TABLE 11 13% 260 3587-17 PROPERTY UNIT 1.IVF 2.IVF WATER.IVF Max cooling rate C./s 177.43 206.23 207.67 Temp at Max C. 663.89 594.26 619.47 Cooling Rate Temp at Start of C. 844.3 800.57 844.21 Boiling Temp at Start of C. 156.28 150.25 57.68 Convection Cooling Rate at C./s 66.26 86.43 95.22 300 C. Time to 600° C. s 2.34 3.94 1.83 Time to 400° C. s 3.83 5.07 2.93 Time to 200° C. s 7.25 7.81 5.31 Theta 1 C. 844.36 800.35 843.97 Theta 2 C. 287.89 222.32 250.31 HP-IVF (oils) 2311.62 2782.5 3194.38 HP-IVF (polymers) 1339.89 1724.5 1874.86 OPERATION PARAMETERS Product Type Various Medium Temp 26 Medium concentration Various Agitation Rate (m/s) Moderate

FIG. 8 shows the curves produced by using product 3587-203-2 in the IVF method. 3587-203-2 is a product of the condensation reaction of Huntsman Jeffamine T 403 (5 moles) with adipic acid (4 moles). Cloud point was cloudy at ambient temperature and on cooling becomes clear. The MW (average) by GPC is 6,240 daltons. Table 12 shows the parameters of the test leading to the curves of FIG. 8.

TABLE 12 13% 260 3587-203 PROPERTY UNIT 1.IVF 2.IVF WATER.IVF Max cooling rate C./s 177.43 195.23 207.67 Temp at Max C. 663.89 600.15 619.47 Cooling Rate Temp at Start of C. 844.3 816.1 844.21 Boiling Temp at Start of C. 156.28 144.06 57.68 Convection Cooling Rate at C./s 66.26 82.02 95.22 300 C. Time to 600° C. s 2.34 3.47 1.83 Time to 400° C. s 3.83 4.69 2.93 Time to 200° C. s 7.25 7.69 5.31 Theta 1 C. 844.36 814.56 843.97 Theta 2 C. 287.89 237.98 250.31 HP-IVF (oils) 2311.62 2677.11 3194.38 HP-IVF (polymers) 1339.89 1647.1 1874.86 OPERATION PARAMETERS Product Type Various Medium Temp 26 Medium concentration Various Agitation Rate (m/s) Moderate

FIG. 9 shows the curves produced by using product 3533-171-1 in the IVF method. 3533-171-1 is the product of the condensation reaction of Huntsman Jeffamine T 403 (2 moles) with adipic acid (1 mole) with about 12% water added when the reaction is cooled below 90° C. The water acts as a solvent to reduce the viscosity of the neat product to make it more flowable. Cloud point, about 88° Fahrenheit. Table 13 shows the parameters of the test leading to the curves of FIG. 9.

TABLE 13 13% 260 3533-171 PROPERTY UNIT 1.IVF 1.IVF WATER.IVF Max cooling rate C./s 177.43 215.84 207.67 Temp at Max C. 663.89 595.46 619.47 Cooling Rate Temp at Start of C. 844.3 834.04 844.21 Boiling Temp at Start of C. 156.28 143.43 57.68 Convection Cooling Rate at C./s 66.26 90.94 95.22 300 C. Time to 600° C. s 2.34 2.7 1.83 Time to 400° C. s 3.83 3.82 2.93 Time to 200° C. s 7.25 6.38 5.31 Theta 1 C. 844.36 832.65 843.97 Theta 2 C. 287.89 238.26 250.31 HP-IVF (oils) 2311.62 2922.34 3194.38 HP-IVF (polymers) 1339.89 1795.53 1874.86 OPERATION PARAMETERS Product Type Various Medium Temp 26 Medium concentration Various Agitation Rate (m/s) Moderate

All publications cited in this specification and U.S. provisional patent application No. 62/147840, filed Apr. 15, 2015 are incorporated herein by reference. While the invention has been described with reference to particular embodiments, it will be appreciated that modifications can be made without departing from the spirit of the invention. Such modifications are intended to fall within the scope of the appended claims. 

1. A composition comprising a polyamidopolyamine produced by the reaction of a polybasic acid and primary polyamine, which is linear, cyclic, branched or cross-linked, said polyamidopolyamine having a molecular weight of about 500 to about 100,000 and having one or more repeating pendant amino groups
 2. The composition according to claim 1, further comprising one or more of: (a) a polyamidopolyamine that comprises an imide group; (b) unreacted polyamine; (c) multiple different polyamidopolyamines, (d) multiple different polyamidopolyamines having an imide group, multiple different unreacted polyamines, or any combination thereof.
 3. The composition according to claim 1, wherein said polyamidopolyamine is of the Formula I, Formula II, Formula III, Formula IV, or Formula V.
 4. The composition according to claim 1, wherein said polyamidopolyamine is of the (a) Formula A:

wherein: each polybasic acid is a dimer acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a and a′ are independently 1 or 2; b is 0, 1 or 2; and r is a number between 2 to about 10, including both endpoints of the range; or (b) Formula A′:

wherein a is 1, 2, 3, or 4, and said reaction has a 1:1 molar ratio of polyamine to dimer acid; or (c) Formula B:

wherein: each polybasic acid is a trimer acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a, c, d and e are independently 1 or 2; b is 0, 1 or 2; and r is a number between 3 to about 10, including both endpoints of the range; or (d) Formula C:

wherein: each polybasic acid is a tetrabasic acid; each primary polyamine is independently a diamine, a triamine, or a tetraamine or an amine comprising 5 or more free amino groups; a, c, d, and e are independently 1 or 2; b is 0, 1 or 2; and r is a number between 4 to 10, including both endpoints of the range.
 5. The composition according to claim 1, further comprising (i) an organic hydroxyl containing diluent; or (ii) water as a diluent; or (iii) a water-soluble acid to increase the solubility of the polyamidopolyamine and non-polymeric amidoamine in water
 6. (canceled)
 7. The composition according to claim 1, which is characterized by one of more of: (a) low-foaming, non-foaming, or defoaming properties; (b) antimicrobial or bioresistant properties; (c) lubricating properties; (d) a cloud point of about 25° C. to about 82° C., or of about 77° F. to about 180° F., in water; (e) a pH of about 8 to about 11: (f) water-soluble; and (g) water dispersible.
 8. A method for preparing a composition of claim 1 comprising condensing: (a) a polyamine comprising a primary amino group, and a C₃ to C₁₆ polybasic acid or derivative thereof, optionally in the presence of an organic hydroxyl-containing diluent; or (b) a polyamine comprising three primary amino groups, and a C₃ to C₁₆ polybasic acid or derivative thereof, optionally in the presence of an organic hydroxyl-containing diluent; or (c) two polyamines comprising three amino groups and a C₃ to C₁₆ polybasic acid or derivative thereof; or (d) a polyamine comprising three amino groups and two C₃ to C₁₆ polybasic acids or derivative thereof; or (e) a polyamine comprising three amino groups, a polyamine comprising two amino groups, and a C₃ to C₁₆ polybasic acid or derivative thereof.
 9. A method for preparing a composition comprising a polyamidopolyamine, wherein said method comprises: (a) reacting a polybasic acid with a polyamine and an optional hydroxyl-containing solvent to produce a first polyamidopolyamine as a reaction product; (b) reacting the product (a) with the same or different a polybasic acid and an optional hydroxyl-containing solvent to produce another polyamidopolyamine as a subsequent reaction product; (c) performing additional sequential condensation reactions by reacting the polyamidopolyamine reaction product of each preceding condensation reaction with the same or different polybasic acid and an optional hydroxyl-containing solvent, and (d) terminating the reaction sequence when the composition demonstrates a desired characteristic selected from anti-foaming, defoaming, lubricity, bioresistance, antimicrobial activity or any combination thereof.
 10. The method according to claim 9, further comprising at least one of (e) further terminating additional free amino groups to amide acids or salts with cyclic anhydride to cap amino groups at a temperature below the condensation reaction temperature; (f) adding an organic hydroxyl-containing diluent or solvent at the initiation of the reaction; or (g) adding water or an organic hydroxyl-containing diluent or solvent at the end of the reaction to adjust viscosity of the composition.
 11. The method according to claim 8, wherein the resulting composition comprises a polyamidopolyamine, which is a linear, cyclic, branched or cross-linked amide comprising multiple primary amine groups.
 12. The method according to claim 8, wherein said polybasic acid comprises two C(O)OH groups or derivatives thereof.
 13. The method according to claim 9, wherein said polyamines are different.
 14. The method according to claim 9, further comprising: (a) having a mole ratio of polybasic acid to polyamine is equal to or greater than about 1: (1×), wherein X is the number of C(O)OH groups in the polybasic acid; or (b) having a mole ratio of the polybasic acid to the polyamine is about is about 1:1, with an optional organic hydroxyl-containing solvent.
 15. The method according to claim 8, wherein said polyamine is: (a) triaminononane or 4-aminomethyl-1,8-octanediamine; (b) the formula:

wherein: R¹, R³ and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R⁴ and R⁶ are independently methyl, ethyl, propyl, or butyl; and a, b and c are additively a number between 0 to about 90, including both endpoints of the range; or (c) of the formula:

wherein s, t and u are additively a number between 3 to about 90, including both endpoints of the range; or (d) the formula:

wherein: R¹, is H, methyl, ethyl, propyl or butyl; R², R³, and R⁴ are, independently, methyl, ethyl, propyl, or butyl; and e and f are additively a number between 0 to about 90, including both endpoints of the range; or (e) the formula: NH₂CH(CH₃)CH₂—(O—CH₂CF₂)_(g)—(O—CH₂CH(CH₃))_(h)—(O—CH₂CH(CH₃))—NH₂ wherein g and h are additively a number between 0 to about 90, including both endpoints of the range; or (f) the formula:

wherein: R¹, R³, R⁵ and R⁷ are independently H, methyl, ethyl, propyl or butyl; R², R⁴, R⁶, and R⁸ are independently is methyl, ethyl, propyl, or butyl; and w, j, k and m are additively a number between 0 to about 90, including both endpoints of the range; or (g) the formula:

wherein h, n, o and p are additively a number between 4 to about 90, including both endpoints of the range; or (h) the formula:

wherein: R¹, R^(3,) and R⁵ are independently H, methyl, ethyl, propyl or butyl; R², R^(4,) and R⁶ are independently methyl, ethyl, propyl, or butyl; and a′, b′ and c′ are additively a number between 0 to 90, including both endpoints of the range; or (i) the formula:

wherein e′, f′ and g′ are additively a number between 3 to
 90. 16. A composition comprising a non-polymeric amidoamine, which is a linear or branched amide containing a primary amine group, said non-polymeric amidoamine having a molecular weight of about 290 to about
 5000. 17. The composition according to claim 16, wherein said composition is produced by the reaction of a monobasic acid and a primary amine.
 18. The composition according to claim 16, further comprising an amide comprising a diamide, a triamide or a tetraamide, or a mixture thereof.
 19. The composition according to claim 1, further comprising a non-polymeric amidoamine, which is a linear or branched amide containing a primary amine group, said non-polymeric amidoamine having a molecular weight of about 290 to about
 5000. 20. The composition according to claim 19, wherein said non-polymeric amidoamine is: (a) of the Formula F:

wherein x, y, and z are, are additively a number between 3 to about 90, including both endpoints of the range; and R¹ is C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl; or (b) of the Formula G:

wherein x, y, and z are, additively a number between 3 to about 90, including both endpoints of the range; and R¹, and R² are, independently, C₁ to C₁₁ alkyl or C₁ to C₁₁ substituted alkyl.
 21. A composition of claim 1, produced by a condensation reaction wherein the reactants comprise an acid and a polyamine, wherein the acid is a polybasic acid, a monobasic acid, or both a polybasic acid and a monobasic acid, in the optional presence of an organic hydroxyl-containing diluent. 